CN103721749B - Avoid composite catalyst and the application thereof of fouling in production of biodiesel - Google Patents
Avoid composite catalyst and the application thereof of fouling in production of biodiesel Download PDFInfo
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- CN103721749B CN103721749B CN201310746397.4A CN201310746397A CN103721749B CN 103721749 B CN103721749 B CN 103721749B CN 201310746397 A CN201310746397 A CN 201310746397A CN 103721749 B CN103721749 B CN 103721749B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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Abstract
The invention provides a kind of composite catalyst avoiding fouling plugging in production of biodiesel, composite catalyst comprises diethylenetriamine pentaacetic acid 3% ~ 20%, ethylenediamine tetra-acetic acid 3% ~ 20%, ATMP 3% ~ 15%, HEDP 3% ~ 15%, potassium hydroxide 30% ~ 60%, the host of NaOH 30% ~ 60%, and monoethanolamine and methyl alcohol are as auxiliary agent.The composite catalyst that the present invention proposes is in production biodiesel process, the addition of (traditional handicraft) NaOH is substantially identical, effectively can solve the problem of fouling plugging in product, does not have fouling and clogging pipeline by during discharge of pipes impurity, the liquid of discharging, directly can be used as fuel.Decrease the step of cleaning pipeline on the one hand, improve production efficiency, annual production improves; The fuel obtained on the other hand makes enterprise obtain more economic benefits.
Description
Technical field
The invention belongs to the catalyst field of chemical reaction, be specifically related to the catalyst containing organic compound and application thereof.
Background technology
Biodiesel is the raw matter fuel that raw material (crude oil) is produced by vegetable oil or animal tallow, even waste oil, and a kind of character is similar to the substitute of diesel fuel of diesel oil.
The preparation method of biodiesel can be add in components of biomass by the mineral oil of routine; Or the mixture of vegetable oil and mineral oil forms biodiesel material by hydro-conversion (the industrial production application of CIMCu-Ni oil hydrogenation catalyst, fine chemistry industry, the 16th phase in 1999), isomerization; Because biomass material contains high-caliber fatty acid ester, particularly glyceride, first hydrolysis of ester bonds with is needed also to remove glycerine, then hydrogenation; Or adopt enzymolysis to reach the methods (patent CN102177244A) such as the object of hydrolysis.Hydrogenation reaction needs the reactor of complex and expensive, and hydrogenation catalyst is also expensive, and needs regular regeneration.Because microorganism is insensitive for the character of raw material, higher to the requirement of microorganism when raw material is more complicated.
The biodiesel oil preparing process that the applicant of the application proposes in patent CN102311883A, utilize main component triglyceride generation ester exchange reaction in the alcohols material such as methyl alcohol or ethanol and crude vegetal or animal tallow, utilize the glyceryl on methoxy substitution LCFA, glyceric acid acid esters is fractured into multiple LCFA methyl esters, thus shorten carbon chain lengths, reduce the viscosity of oil plant, improve mobility and the vaporization performance of oil plant, reach the requirement used as fuel.After ester exchange reaction, realize being separated of glycerine and crude fatty acid methyl ester according to the difference of component density each in reactant mixture.The catalyst that the method uses is simple, less demanding to consersion unit.But in this production method, stratification after ester exchange reaction, the maximum impurity of reactant mixture Midst density stays the bottom, discharges in pipeline.In prior art, because raw material contains unsaponifiable matter, fiber, mineral matter etc., after reaction, produce the inorganic salts of inorganic salts especially indissoluble, form incrustation, finally block pipeline.Just need at set intervals to clear up pipeline, cause production efficiency to decline.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, propose a kind of composite catalyst avoiding fouling in production of biodiesel.
Another object of the present invention is the preparation method proposing this composite catalyst.
3rd object of the present invention is the application proposing described composite catalyst.
The technical scheme realizing above-mentioned purpose of the present invention is:
Avoid a composite catalyst for fouling in production of biodiesel, be made up of host and auxiliary agent, the host of described composite catalyst comprises the composition of following percentage by weight:
Auxiliary agent is monoethanolamine and methyl alcohol;
Wherein ATMP is the solution of concentration 45.0-55.0%, and HEDP is the solution of concentration 50-68%.
Preferably, the host of described composite catalyst comprises the composition of following percentage by weight:
Wherein, auxiliary agent monoethanolamine and methanol usage are not particularly limited, and can add more or less auxiliary agent, such as host weight 0.01-1 monoethanolamine doubly, 5-100 methyl alcohol doubly.The part by weight of preferred host and auxiliary agent monoethanolamine, methyl alcohol is 1:0.08 ~ 0.18:15 ~ 25.
Prepare a method for described composite catalyst, it comprises step:
By diethylenetriamine pentaacetic acid, ethylenediamine tetra-acetic acid, ATMP, HEDP, mixing, add part methyl alcohol; Potassium hydroxide, NaOH and monoethanolamine mix, and add remaining methyl alcohol.Added by methyl alcohol added by Part I and Part II, there is no particular restriction for methanol ratio, can be the same half, also can Part I is added, Part II adds less.
In order to easy to operate, by diethylenetriamine pentaacetic acid, ethylenediamine tetra-acetic acid, ATMP, HEDP, mixing, the methyl alcohol of 30-80% can be added; Potassium hydroxide, NaOH and monoethanolamine mix, and add remaining methyl alcohol.
The application of composite catalyst of the present invention in production biodiesel.
Particularly, described application, comprises step:
1) by composite catalyst diethylenetriamine pentaacetic acid, ethylenediamine tetra-acetic acid, ATMP, HEDP mixing, methyl alcohol is added; Potassium hydroxide, NaOH mix with monoethanolamine, methyl alcohol, obtain Part I and the Part II of alkaline composite catalyst;
2) crude oil raw material and methanol feedstock mixing concentrated sulfuric acid generation esterification, after esterification, first add Part I and the Part II of described compound base catalyst in backward reactant mixture, the composite catalyst host weight added is 5 ~ 10 ‰ of crude oil raw material weight, and ester exchange reaction occurs;
3) isolate methyl alcohol after reaction, making crude fatty acid methyl ester in reactant mixture, impurity and glycerine layering through leaving standstill, obtaining crude fatty acid methyl ester; The crude fatty acid methyl ester obtained is obtained biodiesel through purification, distillation.
The reaction of above-mentioned preparation of biodiesel is identical with prior art (such as patent CN102311883B).
Wherein, described step 2) in the temperature of reaction be 70-90 DEG C, pH value is 8 ~ 9.As checked, pH value is less than 8, then add a little composite catalyst to pH value 8.The present invention finds in an experiment, and after adding composite catalyst under normal circumstances, namely pH value meets the requirements.
For ease of operation, reduce significant loss, described step 2) in when adding compound base catalyst mixed solution the temperature of preferred reaction system be 60-65 DEG C.
After reaction, the separation of reactant mixture can adopt any means of this area routine, such as, the density of product can be utilized different and be separated: in described step 4), reactant mixture layering after leaving standstill, orlop is impurity, passes through discharge of pipes.
Beneficial effect of the present invention is:
The composite catalyst that the present invention proposes is in production biodiesel process, substantially identical with the addition of NaOH, but effectively can solve the problem of fouling plugging in product, fouling and clogging pipeline is not had by when discharge of pipes bottom impurity, what discharge is the liquid of good fluidity, directly can be used as fuel.Decrease the step of cleaning pipeline on the one hand, improve production efficiency, cause annual production to improve; The fuel obtained on the other hand makes enterprise obtain more economic benefits.
Detailed description of the invention
Following examples further illustrate content of the present invention, but should not be construed as limitation of the present invention.Without departing from the spirit and substance of the case in the present invention, the amendment do the inventive method, step or condition or replacement, all belong to scope of the present invention.
If do not specialize, the conventional means that technological means used in embodiment is well known to those skilled in the art.
In embodiment, host agents useful for same is commercial technical grade reagent.Wherein, ATMP is the solution of mass concentration 48.0-52.0%; HEDP is the solution of mass concentration 60%.Diethylenetriamine pentaacetic acid, ethylenediamine tetra-acetic acid, NaOH, potassium hydroxide are solid.
Embodiment 1
1) mixture alkalescence composite catalyst:
Host is diethylenetriamine pentaacetic acid 10%, ethylenediamine tetra-acetic acid 10%, ATMP 4%, HEDP 6%, potassium hydroxide 30% and NaOH 40%, total amount 40kg.Auxiliary agent is the monoethanolamine of host gross weight 15% and the methyl alcohol of host gross weight 20 times.By diethylenetriamine pentaacetic acid, ethylenediamine tetra-acetic acid, ATMP, HEDP mixing, add half methyl alcohol (composite catalyst Part I); Potassium hydroxide, NaOH, monoethanolamine mix, and add the monoethanolamine of host weight 15% and remaining half methyl alcohol, mix (composite catalyst Part II);
2) biodiesel is prepared:
In advance 1200kg methyl alcohol and the 45kg concentrated sulfuric acid are dropped into ingredients pot, and open stirring.After waste oil 8 tons washing, vacuum dehydration, drop into together with the material in ingredients pot in enamel reaction still, open reacting kettle jacketing and be steam heated to about 70 DEG C, keep 30 minutes.Continue to open and enter steam valve greatly and regulate each valve of methanol eddy, condensed for methanol condenser crude carbinol is recycled to crude carbinol tank.When liquidus temperature reaches 110-115 DEG C, supplement vapor phase methanol, feed rate controls at 500L/h; After 2 hours, sampling detects; During acid value≤2, stop adding of methyl alcohol.
Steam off, when temperature≤65 DEG C of reactor, stir in the composite catalyst Part I input reactor that step 1) is obtained, after 10 minutes, Part II is put in reactor.The pH value of inspection reactant mixture is 8-9.Open steam valve simultaneously, start heating.The temperature of ester exchange reaction controls at 70-80 DEG C, and methyl alcohol carries out total reflux reaction, stirring and refluxing time 2-3h.Then stop backflow, normal pressure reclaims the crude carbinol that evaporates to crude carbinol tank, often pushes back and receives end, steam off valve when reactor temperature is raised to 90-95 DEG C.Crude carbinol discharges material stratification remaining in rear reactor: temperature 95 DEG C, 30 minutes time, vacuum-0.95MPa, upper strata is that crude fatty acid methyl ester (separates, need not wash again and it also avoid dehydration), glycerine is lower floor, and bottom is impurity (not surpassing 3%).
The crude fatty acid methyl ester obtained, under the pressure of-0.099Mpa, is carried out rectifying and is obtained smart fatty acid methyl ester and plant asphalt, by biodiesel cut difference by temperature (a.≤280 DEG C; DEG C b.280 ~ 365 DEG C; DEG C c.365 ~ 380 DEG C; D. >=380 DEG C) segmentation proceed to high-purity lightweight level, middle quality and grade, heavy level fatty acid methyl ester storage tank.
In this biodiesel finished product, the content of fatty acid methyl ester (total amount) is 98.5% after testing, and total glycerol content is 0.21%, density is 860.0, acid number is 0.8, viscosity is 4.1, flash-point is 130, Cetane number is 53, sulfur content is 0.001, methanol content 0.005ppm.
After glycerine separates, the impurity of discharging bottom reactor is the liquid (being mainly pitch, sugar) of good fluidity, can burn.For the enterprise of annual output 20000 tons of biodiesel, reduce the operation of pipeline cleaning, biodiesel processes time decreased amount about 15%, be equivalent to improve annual production 17%(and produce 20000 tons of every 12 hourly outputs of enterprise about 3.33 tons per year, this is every 10 hourly outputs about 3.33 tons from now on).
Embodiment 2
1) mixture composite catalyst: 100%
Host is: the diethylenetriamine pentaacetic acid 15% of part by weight, ethylenediamine tetra-acetic acid 10%, ATMP 5%, HEDP 8%, potassium hydroxide 30%, NaOH 32%.Total amount 40kg.Auxiliary agent is the monoethanolamine of host gross weight 18% and the methyl alcohol of host gross weight 25 times.
By diethylenetriamine pentaacetic acid, ethylenediamine tetra-acetic acid, ATMP, HEDP mixing, add half methyl alcohol (composite catalyst Part I); Potassium hydroxide, NaOH add the monoethanolamine of host weight 18% and remaining half methyl alcohol, mix (composite catalyst Part II).
2) biodiesel is prepared:
Preparation method is with embodiment 1.
In biodiesel finished product, the content of fatty acid methyl ester (total amount) is 98.6% after testing, total glycerol content is 0.22%, and density is 860.0, acid number is 0.8, viscosity is 4.1, flash-point is 130, Cetane number is 53, sulfur content is 0.001, methanol content 0.005ppm.
Embodiment 3
1) mixture alkalescence composite catalyst:
Host: the diethylenetriamine pentaacetic acid 6% of part by weight, ethylenediamine tetra-acetic acid 8%, ATMP 5%, HEDP 8%, potassium hydroxide 30%, NaOH 43%.Total amount 40kg.The monoethanolamine of host gross weight 10% and the methyl alcohol of host gross weight 20 times.
By diethylenetriamine pentaacetic acid, ethylenediamine tetra-acetic acid, ATMP, HEDP mixing, add half methyl alcohol (composite catalyst Part I); Potassium hydroxide, NaOH add the monoethanolamine of host weight 10% and remaining half methyl alcohol, mix (composite catalyst Part II);
2) biodiesel is prepared:
Preparation method is with embodiment 1.
In obtained biodiesel finished product, the content of fatty acid methyl ester (total amount) is 98.9%, total glycerol content is 0.22%, and density is 860.0, acid number is 0.8, viscosity is 4.0, flash-point is 130, Cetane number is 53, sulfur content is 0.001, methanol content 0.005ppm.
Embodiment 4
1) mixture alkalescence composite catalyst:
Add the diethylenetriamine pentaacetic acid 11% of part by weight successively, ethylenediamine tetra-acetic acid 11%, ATMP 3%, HEDP 5%, potassium hydroxide 35%, NaOH 35%.Host total amount 40kg.The monoethanolamine of host gross weight 10% and the methyl alcohol of host gross weight 16 times.
By diethylenetriamine pentaacetic acid, ethylenediamine tetra-acetic acid, ATMP, HEDP mixing, add half methyl alcohol (composite catalyst Part I); Potassium hydroxide, NaOH add the monoethanolamine of host weight 10% and remaining half methyl alcohol, mix (composite catalyst Part II);
2) biodiesel is prepared:
Preparation method is with embodiment 1.
In biodiesel finished product, the content of fatty acid methyl ester (total amount) is 98.6% after testing, total glycerol content is 0.22%, and density is 860.0, acid number is 0.8, viscosity is 4.1, flash-point is 130, Cetane number is 53, sulfur content is 0.001, methanol content 0.005ppm.The impurity of discharging is the liquid of good fluidity, can burn.For the enterprise of annual output 20000 tons of biodiesel, reduce the operation of pipeline cleaning, biodiesel processes time decreased amount about 21%, be equivalent to improve annual production 26%.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (5)
1. avoid a composite catalyst for fouling in production of biodiesel, it is characterized in that, be made up of host and auxiliary agent, the host of described composite catalyst is grouped into by the one-tenth of following percentage by weight:
The part by weight of the host of described composite catalyst and auxiliary agent monoethanolamine, methyl alcohol is 1:0.08 ~ 0.18:15 ~ 25;
Described composite catalyst adopts following methods preparation:
By diethylenetriamine pentaacetic acid, ethylenediamine tetra-acetic acid, ATMP, HEDP mixing, add the methyl alcohol of 30-80%; Potassium hydroxide, NaOH and monoethanolamine mix, and add remaining methyl alcohol.
2. the application of composite catalyst described in claim 1 in production biodiesel, comprises step:
1) by diethylenetriamine pentaacetic acid, ethylenediamine tetra-acetic acid, ATMP, HEDP mixing, methyl alcohol is added; Potassium hydroxide, NaOH mix with monoethanolamine, methyl alcohol, obtain Part I and the Part II of alkaline composite catalyst;
2) crude oil raw material and methanol feedstock mixing concentrated sulfuric acid generation esterification, after esterification, first add Part I and the Part II of described compound base catalyst in backward reactant mixture, the composite catalyst host weight added is 5 ~ 10 ‰ of crude oil raw material weight, and ester exchange reaction occurs;
3) isolate methyl alcohol after reaction, making crude fatty acid methyl ester in reactant mixture, glycerine and impurity layering through leaving standstill, obtaining crude fatty acid methyl ester; The crude fatty acid methyl ester obtained is obtained biodiesel through purification, distillation.
3. application according to claim 2, is characterized in that, described step 2) in reaction temperature be 70 ~ 90 DEG C, pH value is 8 ~ 9.
4. application according to claim 2, is characterized in that, described step 2) in when adding compound base catalyst mixed solution the temperature of reaction system be 60 ~ 65 DEG C.
5. application according to claim 2, is characterized in that, described step 3) in, reactant mixture layering after leaving standstill, orlop is impurity, passes through discharge of pipes.
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| EP3504300A1 (en) | 2016-08-25 | 2019-07-03 | General Electric Company | Reduced fouling of hydrocarbon oil |
| CN110437937B (en) * | 2019-08-30 | 2022-10-25 | 河北复亚能源科技有限公司 | Synthesis method of environment-friendly biodiesel for vehicles |
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| CN102311883A (en) * | 2011-08-10 | 2012-01-11 | 北京清研利华石油化学技术有限公司 | Method for preparing high-purity biodiesel |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102311883A (en) * | 2011-08-10 | 2012-01-11 | 北京清研利华石油化学技术有限公司 | Method for preparing high-purity biodiesel |
Non-Patent Citations (1)
| Title |
|---|
| 柴油加氢精制阻垢剂的开发;潘延民 等;《河南石油》;20030331;第17卷(第2期);第59页第1节，第60页第3.1节 * |
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