CN102989440A - Modified kaliophilite biodiesel solid alkaline catalyst and production process thereof - Google Patents
Modified kaliophilite biodiesel solid alkaline catalyst and production process thereof Download PDFInfo
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- CN102989440A CN102989440A CN2012105382037A CN201210538203A CN102989440A CN 102989440 A CN102989440 A CN 102989440A CN 2012105382037 A CN2012105382037 A CN 2012105382037A CN 201210538203 A CN201210538203 A CN 201210538203A CN 102989440 A CN102989440 A CN 102989440A
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- kaliophilite
- biodiesel
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Abstract
The invention relates to an alkaline solid catalyst, and particularly relates to kaliophilite capable of being used in process for preparing biodiesel via catalyzing ester exchange. The components mainly comprise, by weight, 1-5 parts of Li, 40-47 parts of K2O, 20-26 parts of Al2O3 and 27-30 parts of SiO2. The kaliophilite is prepared by using a coprecipitation method and an impregnation method in sequence via drying and baking processes. Compared with a convention method for preparing the kaliophilite in present industry, the method prepared by the invention has finer particles, more uniform chemical components and higher catalytic activity. The active sites of the kaliophilite are not easy to lose.
Description
?
Technical field:
What the present invention relates to is a kind of alkali solid catalyst, and especially a kind of catalytic transesterification that can be used for prepares kaliophilite in the biodiesel processes.
Background technology:
Biodiesel mainly refers to pass through the fatty acid ester that ester exchange reaction makes with animal and plant fat and low-carbon alcohols (methyl alcohol or ethanol), and its theory index is similar to common mineral diesel, is desirable the substituting of petrifaction diesel
Product, it can directly mix with petrifaction diesel, and CO, SO
2Obviously reduce Deng the toxic gas discharging.
The industrial production of biodiesel mainly is to utilize the homogeneous phase base catalysis techniques such as KOH or NaOH at present, but
Be that catalyst can not be recycled, its product neutralization, water-washing process will consume a large amount of energy, and produce the waste liquor contamination environment, and solid base catalyst can overcome above-mentioned shortcoming effectively, thereby becomes research emphasis
The field.
Kaliophilite (KAlSi0
4) potassium high temperature in the lattice is difficult for running off, and has been developed to catalyst promoter, is applicable to the petroleum chemical industries such as synthetic ammonia, ethyl benzene dehydrogenation preparation of styrene and producing hydrogen from steam conversion of hydrocarbons.
Because it is insoluble to oil, pure and mildly has certain basic active center, therefore also satisfy the condition of catalysis for preparing biodiesel oil catalyst.
1000 ℃ of calcined coke jewel Al of the normal employing of industry preparation kaliophilite
20
32Si0
22H
20 and KOH(or K
2C0
3) method, but its product particle is large and the chemical composition heterogeneity, and it is low to be used for the synthetic oil productivity of biodiesel.
Summary of the invention:
The present invention is directed to the existing deficiency of prior art, provide a kind of employing coprecipitation sol-gel system to synthesize the kaliophilite technical scheme.
This programme is achieved by the following technical measures:
Kaliophilite provided by the invention mainly is potassium silicate, 18.0-54.0 potassium hydroxide, 28.5-85.5 ANN aluminium nitrate nonahydrate coprecipitation drying, the synthetic kaliophilite of roasting of 3.5-10.5 by weight portion, with infusion process doping weight portion 1-5 lithium chloride, make the modification kaliophilite afterwards.
Its component mainly comprises Li 1-5, K according to weight portion
2O 40-47, Al
2O
320-26, SiO
227-30.
Its preparation method is: the 0.3 mol/L potassium silicate solution of 0.15-0.45 L is mixed with the 2.0mol/L potassium hydroxide solution of 3.0-9.0L, under the magnetic agitation effect, splash into the 1.0 mol/L ANN aluminium nitrate nonahydrate solution of 0.5-1.5L, the control pH of mixed is that the 10.5-13.5. mixed liquor is at 20-40 ℃ of ageing 0.5-5.0 h, wash 100-150 ℃ of lower dry 2.0-6.0h, then at 900-1200 ℃ of lower roasting 0.5-4.0 h, the lithium chloride solution that adds the 0.5mol/L of 0.2-0.6L, after fully mixing, 100-150 ℃ of dry 4-10h, and at 400-560 ℃ of roasting 1.0-5.5h.
The catalyst that makes is used on the fixed bed reactors, and under 100 ℃, catalytic alcohol and oil react, and methyl alcohol evaporates and enters condenser and reclaims after the reaction, and biodiesel and glycerine are by regularly collection of outlet.Reaction yield is analyzed with HP GC5890, and capillary column is that (30 m * 0.15mm), carrier gas (nitrogen) flow is 0.9 mL/min to hp-innowax, split ratio 10:1.Begin with speed 10 from room temperature
oC/min heats up, and injector temperature is 250
oC, detector temperature are 300
oC.The internal standard compound methyl margarate is dissolved in the n-hexane concentration 4 mg/L.Sample thief 4 μ L, be dissolved in the 300 μ L n-hexanes, add again the hexane solution that 100 μ L are dissolved with internal standard compound, get after mixing in the 2 μ L injecting chromatographs and analyze, survey its biodiesel production rate, demarcate its active sites loss power with the number of times that recycles of solid catalyst.
The beneficial effect of this programme can be learnt according to the narration to such scheme, owing in this scheme, adopt the synthetic kaliophilite of coprecipitation sol-gel system, to compare particle thinner with the preparation method of preparation kaliophilite in the present industry, chemical composition is homogeneous more, catalytic activity is higher, and can better reduce the loss of active sites through the use of experimental verification lithium chloride.
This shows that the present invention compared with prior art has outstanding substantive distinguishing features and significant progressive, the beneficial effect of its enforcement also is apparent.
The specific embodiment:
For clearly demonstrating the technical characterstic of this programme, below by the specific embodiment, this programme is set forth.
Embodiment one
Get the kaliophilite catalyst of present commercial run preparation, it consists of 29.7%K
2O, 32.3%Al
2O
3, 38.0%SiO
2Under this catalyst is used for 100 ℃ at the fixed bed reactors catalysis for preparing biodiesel oil, fixed bed reactors pipe range 112 mm, diameter 14 mm, squeezed pillared catalyst is loaded in the reaction tube at random, two ends seal with stainless (steel) wire, prevent the catalyst seepage.The alcohol of preheating, oil content are not delivered in the reactor tube by certain flow by high-pressure pump, fully contact with catalyst, and methyl alcohol evaporates and enters condenser and reclaims after the reaction, and biodiesel and glycerine are by regularly collection of outlet.
Productive rate is analyzed with HP GC5890, and capillary column is that (30 m * 0.15mm), carrier gas (nitrogen) flow is 0.9 mL/min to hp-innowax, split ratio 10:1.Begin with speed 10 from room temperature
oC/min heats up, and injector temperature is 250
oC, detector temperature are 300
oC.The internal standard compound methyl margarate is dissolved in the n-hexane concentration 4 mg/L.Sample thief 4 μ L are dissolved in the 300 μ L n-hexanes, add the hexane solution that 100 μ L are dissolved with internal standard compound again, get after mixing in the 2 μ L injecting chromatographs and analyze biodiesel production rate.
Circulation catalysis is recorded the cycle-index that biodiesel production rate is down to a half several times.
Embodiment two
According to method provided by the invention, preparation modification kaliophilite catalyst, its composition is Li 2.3, K by weight
2O 44.7, Al
2O
324.2, SiO
228.8 the catalysis for preparing biodiesel oil condition is identical with embodiment one with detection diesel yield and cycling condition.
Embodiment three
According to method provided by the invention, preparation modification kaliophilite catalyst, its composition is Li 3.7, K by weight
2O 44.1, Al
2O
323.9, SiO
228.3 the catalysis for preparing biodiesel oil condition is identical with embodiment one with detection diesel yield and cycling condition.
Embodiment four
According to method provided by the invention, preparation modification kaliophilite catalyst, its composition is Li 4.7, K by weight
2O 43.6, Al
2O
323.6, SiO
228.1 the catalysis for preparing biodiesel oil condition is identical with embodiment one with detection diesel yield and cycling condition.
The performance comparison of each embodiment catalyst of table 1
As can be seen from Table 1, the biologically active of kaliophilite preparation method provided by the invention obtains kaliophilite far above present industrial production process, and active sites is difficult for running off.
The present invention is not limited in the above-mentioned specific embodiment, and the variation that those of ordinary skills make in essential scope of the present invention, remodeling, interpolation or replacement also should belong to protection scope of the present invention.
Claims (2)
1. a modification kaliophilite biodiesel solid base catalyst is characterized in that the component of this kaliophilite mainly contains by weight: Li 1-5, K
2O 40-47, Al
2O
320-26, SiO
227-30.
2. modification kaliophilite biodiesel solid base catalyst according to claim 1, it is characterized in that, the preparation method of this kaliophilite is: the 0.3 mol/L potassium silicate solution of 0.15-0.45 L is mixed with the 2.0mol/L potassium hydroxide solution of 3.0-9.0L, under the magnetic agitation effect, splash into the 1.0 mol/L ANN aluminium nitrate nonahydrate solution of 0.5-1.5L, the control pH of mixed is that the 10.5-13.5. mixed liquor is at 20-40 ℃ of ageing 0.5-5.0 h, wash 100-150 ℃ of lower dry 2.0-6.0h, then at 900-1200 ℃ of lower roasting 0.5-4.0 h, the lithium chloride solution that adds the 0.5mol/L of 0.2-0.6L, after fully mixing, 100-150 ℃ of dry 4-10h, and at 400-560 ℃ of roasting 1.0-5.5h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012105382037A CN102989440A (en) | 2012-12-13 | 2012-12-13 | Modified kaliophilite biodiesel solid alkaline catalyst and production process thereof |
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|---|---|---|---|
| CN2012105382037A CN102989440A (en) | 2012-12-13 | 2012-12-13 | Modified kaliophilite biodiesel solid alkaline catalyst and production process thereof |
Publications (1)
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|---|---|
| CN102989440A true CN102989440A (en) | 2013-03-27 |
Family
ID=47918845
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107029695A (en) * | 2017-05-14 | 2017-08-11 | 陈毅忠 | A kind of biodiesel prepares the preparation method of special solid base catalyst |
| CN109012646A (en) * | 2018-07-27 | 2018-12-18 | 西安建筑科技大学 | It is used to prepare the low-temperature synthetic method of the kaliophilite catalyst of biodiesel |
-
2012
- 2012-12-13 CN CN2012105382037A patent/CN102989440A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107029695A (en) * | 2017-05-14 | 2017-08-11 | 陈毅忠 | A kind of biodiesel prepares the preparation method of special solid base catalyst |
| CN109012646A (en) * | 2018-07-27 | 2018-12-18 | 西安建筑科技大学 | It is used to prepare the low-temperature synthetic method of the kaliophilite catalyst of biodiesel |
| CN109012646B (en) * | 2018-07-27 | 2021-01-08 | 西安建筑科技大学 | Low-temperature synthesis method of kaliophilite catalyst for preparing biodiesel |
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Application publication date: 20130327 |