CN1836772A - Load type calcium oxide catalyst, its preparation method and uses - Google Patents

Load type calcium oxide catalyst, its preparation method and uses Download PDF

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CN1836772A
CN1836772A CNA2005100556795A CN200510055679A CN1836772A CN 1836772 A CN1836772 A CN 1836772A CN A2005100556795 A CNA2005100556795 A CN A2005100556795A CN 200510055679 A CN200510055679 A CN 200510055679A CN 1836772 A CN1836772 A CN 1836772A
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catalyst
calcium
calcium oxide
carrier
soluble
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CN100357022C (en
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颜姝丽
梁斌
杜泽学
胡见波
王广欣
闵恩泽
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Sichuan University
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sichuan University
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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 present invention provides one kind of supported calcium oxide catalyst and its preparation process and usage in preparing biological diesel oil. The supported calcium oxide catalyst has the co-catalyst of strontium oxide, zinc oxide or lanthanum oxide, carrier of magnesia, silica, alumina or magnesia-alumina, calcium oxide supporting amount of 2-30 wt% of the carrier and co-catalyst supporting amount of 0-16 wt% of the carrier. The supported calcium oxide catalyst has simple preparation process, high repeatability, high reaction activity for preparing biological diesel oil, insolubility in methanol system and easy separation from the reaction system.

Description

Load type calcium oxide catalyst, its preparation method and application
Technical field
The present invention relates to a kind of load type calcium oxide solid base catalyst that is used for the production biodiesel.
Background technology
Biodiesel is the LCFA methyl esters that obtains after natural oil and methyl alcohol (or ethanol) ester exchange reaction, and its combustibility and petroleum diesel are suitable.The Cetane number height of biodiesel does not contain sulfur dioxide in the waste gas of burning back, compares with petroleum diesel, and granular material discharged reduction by 10.1%, hydrocarbon reduce by 21.1%, CO reduces by 11.0%, is eco-friendly vehicle fuel.
The production method of present industrial biodiesel mainly is a liquid catalytic, and it is refining that the raw material animal and plant fat at first carries out strictness, again with some short chain alcohol (methyl alcohol, ethanol etc.) at liquid highly basic (as KOH, NaOH, NaOCH 3Deng) or liquid strong acid (as H 2SO 4Deng) existence under, ester exchange reaction takes place.The shortcoming of this method is that catalyst is not easy to separate with product, and the alkali or the sour weak solution that remain in the product must be removed with a large amount of water washings, thereby produces a large amount of alkalescence (or acid) waste water.Catalyst is discharged with product, can not recycle.A large amount of washes are sneaked into the sugar water phase, and by-product glycerin reclaims difficulty.Liquid acid catalyst causes colloid to generate easily and makes product be brown.When liquid highly basic is made catalyst, influence product with free fatty formation soap easily and separate.Simultaneously, highly basic or acid as catalyst require high to the corrosion resistance of equipment.
Solid catalyst can solve the separation problem that liquid catalyst brings well, can effectively improve the quality of products, and reduces separation costs, avoids discharge of wastewater.The solid catalyst of having reported has solid acid catalyst (as molecular sieve, ion exchange resin, metal phosphate, STANNOUS SULPHATE CRYSTALLINE, zirconia and wolframic acid zirconium etc.), load enzyme catalyst (as lipase etc.), solid base catalyst is (as organic base, the carrying alkali metal hydroxide (NaOH, KOH) etc.) of load.
Gryglewicz has introduced in the article that Bioresource Technology 70 (1999) 249-253 deliver and has used different catalysts to prepare the method for rapeseed methylester, and alkaline earth series oxide, hydroxide and methoxylation compounds such as magnesium, calcium and barium tested in the catalytic activity of rapeseed oil methyl alcohol ester-exchange reaction, active order is: NaOH＞Ba (OH) 2＞Ca (MeO) 2＞CaO, Mg (OH) 2And Ca (OH) 2Reaction conversion ratio is lower.And Ba (OH) 2Be soluble in methyl alcohol and solution is poisonous, cause the loss of catalyst easily; Though CaO has the certain reaction activity, mechanical strength is low, forms suspension colloid in alcohol-oily reaction system, is difficult to separate.
Wu Yuxiu etc. (" petrochemical industry ", 32 (9) 2003,800) have reported that adopting with the hydrotalcite is that the Mg-Al composite oxide catalysts of precursor is used for the rapeseed oil ester exchange reaction.Studies show that such catalyst has catalytic activity preferably, but hydrotalcite structure complexity, big, the poor repeatability of preparation difficulty, to the free acid in the grease and moisture and airborne CO 2All very sensitive with moisture, poison easily.
Summary of the invention
For solving in the industrial production and the deficiency of the catalyst in the bibliographical information, the invention provides a kind of load type calcium oxide solid base catalyst and preparation method thereof, and the method that adopts this biodiesel.
Catalyst provided by the invention is major catalyst with the calcium oxide, to be selected from strontium oxide strontia (SrO), zinc oxide (ZnO) and lanthana (La 2O 3) metal oxide be co-catalyst, to be selected from magnesia (MgO), silica (SiO 2), aluminium oxide (Al 2O 3) and oxidation magnalium (MgAlO 2) oxide be carrier.Wherein, be 100% in the carrier gross weight, the load capacity of calcium oxide is 2～30 (wt) %, the load capacity of co-catalyst is 0～16 (wt) %.
Calcium oxide load capacity preferred 5～25 (wt) %, the co-catalyst load capacity is preferably 1～10 (wt) %.
Preparation of catalysts method provided by the invention comprises:
1: the carrier that will be selected from magnesia, silica, aluminium oxide and oxidation magnalium obtains pretreated carrier in 400～800 ℃ of oven dry;
2: with the pretreated carrier of the soluble-salt solution impregnation step 1 of calcium, dry, calcining obtains the catalyst precarsor of load calcic component;
3: with catalyst precarsor 300～900 ℃ of activation down in nitrogen atmosphere, obtaining the calcium oxide load capacity is the catalyst of 2～30 (wt) %.
All right load auxiliary agent in the catalyst provided by the invention, the preparation method is with being selected from the soluble-salt solution impregnation of strontium (Sr), zinc (Zn), lanthanum (La) element through the pretreated carrier of step 1, dry, calcining, the load capacity that obtains co-catalyst is the catalyst intermediate of 1～16 (wt) %, and then with this catalyst intermediate of soluble-salt solution impregnation of calcium, according to above-mentioned steps 2,3 dryings, calcining, activation.
Specifically, catalyst provided by the invention can prepare in such a way:
1. the carrier that will be selected from magnesia, silica, aluminium oxide and oxidation magnalium is in 400～800 ℃, preferred 400～500 ℃ of preliminary treatment 3～10 hours, preferred 5～8 hours, purpose was the stable carrier lattice structure and removes some organic impurities, obtains pretreated carrier.
2. with being selected from the soluble-salt solution impregnation of strontium, zinc and lanthanum element through pretreated carrier, in 60～140 ℃, preferred 80～120 ℃ of dryings 3～10 hours are afterwards in 500～1000 ℃ again, calcined 3～15 hours, and obtained the catalyst intermediate of load cocatalyst for preferred 500～700 ℃.Dipping process preferably adopts equi-volume impregnating.
Can not save this step during load cocatalyst.
3. with the pretreated carrier of the soluble-salt solution impregnation step 1 of calcium or the catalyst intermediate of step 2, in 60～140 ℃, preferred 80～120 ℃ of dryings 3～12 hours, afterwards in 270～1000 ℃, calcined 5～12 hours, and obtained the catalyst precarsor of load calcic component for preferred 500～700 ℃.Dipping process preferably adopts equi-volume impregnating.
4. with catalyst precarsor before use, in nitrogen atmosphere 300～900 ℃, preferred 500～800 ℃ of activation 1～5 hour down make the calcium group resolve into calcium oxide, and obtaining the calcium oxide load capacity is 2～30 (wt) %, the catalyst of preferred 5～25 (wt) %.
The described preferred strontium nitrate solution of soluble-salt solution, zinc nitrate solution, the lanthanum nitrate hexahydrate that is selected from strontium, zinc and lanthanum element, solution concentration can be 1～15 (wt) %.
The preferred calcium acetate solution of soluble-salt solution or the calcium nitrate solution of described calcium, solution concentration can be 2～30 (wt) %, preferred 5～25 (wt) %.
The application process of load type calcium oxide catalyst provided by the invention is with its catalyst as the preparation biodiesel.
This application process comprises: in the presence of load type calcium oxide catalyst, grease is mixed with low-carbon alcohols and carry out ester exchange reaction, separate, collect fatty acid ester of low-carbon alcohol, obtain biodiesel.
Described grease is an animal and plant fat, i.e. fatty acid triglyceride, and wherein, the carbon number of aliphatic hydrocarbyl is 6～24, and is preferred 8～22, can contain 0～5 two key in the aliphatic hydrocarbyl, the carbon number of three aliphatic hydrocarbyls can be identical or different.The source of grease can be a vegetable fat, as soybean oil, rapeseed oil, peanut oil, sunflower seed oil, palm oil, coconut oil and the material that contains fat-based that comes from fruit, stem, leaf, limb and the root of other various crops and wild plant; Can also be various animal fats, as lard, butter, sheep oil, fish oil etc.; Also comprise in addition from the oil plant in the materials such as microorganism, algae; Even also comprise frying oil, rotten waste oil etc.Although do not wish,, resembling impurity such as water, phosphatide, colloid, protein, sterol, phenols, vitamin and various pigments is to allow to exist in raw material.In various greases, preferably vegetable oil, particularly rapeseed oil.
Described low-carbon alcohols is meant the fatty alcohol of carbon number between 1～5, can be saturated alcohols or unsaturated alcohol.As methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, allyl alcohol, n-butanol and isomers thereof, amylalcohol and isomers thereof etc.Can use single alcohol or their mixture.Described low-carbon alcohols particular methanol and ethanol.
During reaction, the mole mixture ratio of grease and low-carbon alcohols is 1: 3～1: 40, preferred 1: 6～1: 18.Reaction temperature can be 0～100 ℃, preferred 25～80 ℃.The consumption of calcium oxide catalyst is 0.5～20 (wt) % of grease weight, preferred 1～5 (wt) %.Reaction is preferably under agitation carried out, and along with the prolongation in reaction time, reaction conversion ratio can increase to some extent, and the suitable reaction time is 0.5-24 hour.After reaction is finished, remove by filter catalyst, with the filtrate standing demix, the upper strata is a purpose product fatty acid ester of low-carbon alcohol, and lower floor is a by-product glycerin.
Load type calcium oxide solid base catalyst preparation technology provided by the invention is simple, good reproducibility.When this catalyst is used to prepare biodiesel, reactivity is preferably arranged, and be insoluble to methanol system, separate from reaction system easily.
The specific embodiment
Embodiment 1
Take by weighing 40g MgO in 400 ℃ of calcining 5hr.The calcium acetate solution of preparation 22.6 (wt) %, incipient impregnation are on it, and the dipping number of times is 1 time, in 80 ℃ of dry 10hr,, must contain the catalyst Precursors of Ca afterwards in 700 ℃ of calcining 10hr, get this catalyst Precursors 1g in 700 ℃, nitrogen atmosphere is handled 2hr, gets the load calcium oxide catalyst.(this catalyst called after Y1).
Embodiment 2-9
Preparation process is with embodiment 1, and parameter sees Table 1.
Table 1. Preparation of Catalyst
Embodiment The catalyst numbering Carrier Calcium oxide load capacity (wt) % Calcium salt soln concentration (wt) % Drying condition Calcination condition Activation condition
1 Y1 MgO 24 Calcium acetate 22.6 80℃ 10hr 700℃， 10hr 700℃ N 2，2hr
2 Y2 MgO 18 Calcium acetate 17.8 80℃ 10hr 500℃ 10hr 500℃ N 2，2hr
3 Y3 MgO 10 Calcium acetate 11.3 80℃ 10hr 300℃ 10hr 300℃ N 2，2hr
4 Y4 MgO 6 Calcium acetate 7.8 80℃ 10hr 900℃ 10hr 900℃ N 2，2hr
5 S1 SiO 2 9 Calcium acetate 22.6 80℃ 10hr 700℃ 10hr 700℃ N 2，2hr
6 A1 Al 2O 3 14 Calcium acetate 22.6 80℃ 10hr 700℃ 10hr 700℃ N 2，2hr
7 C1 MgAlO 2 10 Calcium acetate 22.6 80℃ 10hr 700℃ 10hr 700℃ N 2，2hr
8 N1 MgO 17 Calcium nitrate 22.3 80℃ 10hr 700℃ 10hr 700℃ N 2，2hr
9 SN1 SiO 2 11 Calcium nitrate 22.3 80℃ 10hr 700℃ 10hr 700℃ N 2，2hr
Embodiment 10
In the reactor of band condensing unit, add reaction raw materials oil 50g, methyl alcohol 41.5g, and the catalyst Y1 of 1g embodiment 1 preparation, 65 ℃ of reaction temperatures are reacted 5hr under the condition of high degree of agitation, remove by filter catalyst.Filtrate is left standstill 2hr, is divided into two-layer.The upper strata is a layer of methylester of fatty acid, and lower floor is light yellow transparent glycerin layer.Feed stock conversion is 92.3%.In filtrate, do not detect the Ca component, can think the stripping of catalyst-free component.
Embodiment 11-18
Preparation process is with embodiment 10, and parameter sees Table 2.
Table 2 biodiesel manufacture
Embodiment The catalyst numbering Grease amount g Alcohol consumption g Catalyst amount g Reaction temperature ℃ Reaction time hr Conversion ratio %
10 Y1 50 41.5 1 65 4 92.3
11 Y2 50 20.5 1 50 18 93.8
12 Y3 30 20.5 1 65 4 75.1
13 Y4 30 20.5 1 65 4 68.1
14 S1 30 20.5 0.5 65 8 93.1
15 A1 30 20.5 2 65 8 48
16 C1 30 20.5 5 40 8 15.3
17 N1 30 20.5 2 65 15 43.2
18 SN1 30 20.5 2 65 15 26
Embodiment 19
Take by weighing 40g MgO in 400 ℃ of calcining 5hr.The strontium nitrate solution of preparation 10 (wt) %, incipient impregnation are on MgO, and the dipping number of times is 2 times.In 80 ℃ of dry 10hr,, must contain the catalyst Precursors of strontium afterwards in 650 ℃ of calcining 10hr.The calcium acetate solution of preparation 17.8 (wt) %, incipient impregnation is on it, in 100 ℃ of dry 10hr, in 700 ℃ of calcining 10hr, must contain the catalyst Precursors of Ca, Sr afterwards, get this catalyst Precursors 1g in 700 ℃, nitrogen atmosphere is handled 2hr, gets calcic system mixed oxide catalyst.(this catalyst called after YS1).
Embodiment 20
In the reactor of band condensing unit, add reaction raw materials oil 30g, methyl alcohol 41.5g, and the catalyst YS1 of 1g embodiment 19 preparations, 65 ℃ of reaction temperatures are reacted 5hr under the condition of high degree of agitation, remove by filter catalyst.Filtrate is left standstill 2hr, is divided into two-layer.The upper strata is a layer of methylester of fatty acid, and lower floor is light yellow transparent glycerin layer.Feed stock conversion is 89.1%.In filtrate, do not detect the Ca component, can think the stripping of catalyst-free component.
Embodiment 21,23
Preparation process is with embodiment 19, and parameter sees Table 3.
Table 3. Preparation of Catalyst
Embodiment The catalyst numbering Carrier Calcium oxide load capacity (wt) % Auxiliary agent load capacity (wt) % Calcium salt soln concentration (wt) % Auxiliary agent precursor concentration (wt) % Drying condition Calcination condition Activation condition
19 YS1 MgO 13 7 Calcium acetate 17.8 Strontium nitrate 10 80 ℃, 10hr; And 100 ℃, 10hr 650℃，10hr； 700℃，10hr 700℃， N 2，2hr
21 YZ1 MgO 15 5 Calcium acetate 17.8 Zinc nitrate 7 80 ℃, 10hr; And 100 ℃, 10hr 500℃，10hr； 700℃，10hr 700℃， N 2，2hr
23 SL1 SiO 2 19 6 Calcium acetate 17.8 Lanthanum nitrate 12 80 ℃, 10hr; And 100 ℃, 10hr 500℃，10hr； 700℃，10hr 700℃， N 2，2hr
Embodiment 22,24
Preparation process is with embodiment 20, and parameter sees Table 4.
Table 4 biodiesel manufacture
Embodiment The catalyst numbering Grease amount g Alcohol consumption g Catalyst amount g Reaction temperature ℃ Reaction time hr Conversion ratio %
20 YS1 30 41.5 1 65 5 89.1
22 YZ1 30 41.5 2 50 15 71.3
24 SL1 30 41.5 0.5 65 15 83.2
Embodiment 25
Take by weighing 40g Al 2O 3In 400 ℃ of calcining 5hr.The lanthanum nitrate hexahydrate of zinc nitrate solution and 12 (wt) % of preparation 7 (wt) % is that 1: 1 mixed solution incipient impregnation is in Al with volume ratio 2O 3On.In 80 ℃ of dry 10hr,, must contain the catalyst Precursors of Zn, La afterwards in 500 ℃ of calcining 10hr.The calcium acetate solution of preparation 17.8% (wt), incipient impregnation is on it, in 100 ℃ of dry 10hr, afterwards in 700 ℃ of calcining 10hr, the catalyst Precursors that must contain Ca, Zn, La oxide, get this catalyst Precursors 1g in 700 ℃, nitrogen atmosphere is handled 2hr, gets calcic system mixed oxide catalyst CZL1.
Embodiment 26
In the reactor of band condensing unit, add reaction raw materials oil 30g, methyl alcohol 41.5g, and the catalyst CZL1 of 1g embodiment 25 preparations, 65 ℃ of reaction temperatures are reacted 15hr under the condition of high degree of agitation, remove by filter catalyst.Filtrate is left standstill 2hr, is divided into two-layer.The upper strata is a layer of methylester of fatty acid, and lower floor is light yellow transparent glycerin layer.Feed stock conversion is 47%.In filtrate, do not detect the Ca component, can think the stripping of catalyst-free component.

Claims (18)

1. load type calcium oxide catalyst, with the metal oxide that is selected from strontium oxide strontia, zinc oxide and lanthana is co-catalyst, with the oxide that is selected from magnesia, silica, aluminium oxide and oxidation magnalium is carrier, wherein, in the carrier gross weight is 100%, the load capacity of calcium oxide is 2～30 (wt) %, and the load capacity of co-catalyst is 0～16 (wt) %.
2. according to the described catalyst of claim 1, it is characterized in that the load capacity of calcium oxide is 5～25 (wt) %, the load capacity of co-catalyst is 1～10 (wt) %.
3. the preparation method of the described load type calcium oxide catalyst of claim 1 comprises:
1) carrier that will be selected from magnesia, silica, aluminium oxide and oxidation magnalium obtains pretreated carrier in 400～800 ℃ of calcinings;
2) with the pretreated carrier of the soluble-salt solution impregnation step 1 of calcium, dry, calcining obtains the catalyst precarsor of load calcic component;
3) with catalyst precarsor 300～900 ℃ of activation down in nitrogen atmosphere, obtain load type calcium oxide catalyst.
4. according to the described preparation method of claim 3, it is characterized in that, with carrier in 400～500 ℃ of preliminary treatment 3～10 hours.
5. according to the described preparation method of claim 3, it is characterized in that step 2 is with the pretreated carrier of soluble-salt solution impregnation step 1 of calcium, in 60～140 ℃ of dryings, afterwards in 270～1000 ℃ of calcinings.
6. according to the described preparation method of claim 5, it is characterized in that step 2 is 80～120 ℃ of dryings 3～12 hours, 500～700 ℃ of calcinings 5～12 hours.
7. according to the described preparation method of claim 3, it is characterized in that step 3 activates 1～5 hour under 500～800 ℃ in nitrogen atmosphere.
8. according to the described preparation method of claim 3, it is characterized in that the soluble-salt solution of described calcium is calcium acetate solution or calcium nitrate solution, the concentration of solution is 2～30 (wt) %.
9. according to the described preparation method of claim 8, it is characterized in that the concentration of the soluble-salt solution of described calcium is 5～25 (wt) %.
10. according to the described preparation method of claim 3, it is characterized in that, after step 1, also with being selected from the soluble-salt solution impregnation of strontium, zinc and lanthanum element through the pretreated carrier of step 1, in 60～140 ℃ of dryings, in 500～1000 ℃ of calcinings, obtain catalyst intermediate, with this intermediate of soluble-salt solution impregnation of calcium.
11. according to the described preparation method of claim 10, it is characterized in that, with the soluble-salt solution impregnation that is selected from strontium, zinc and lanthanum element through pretreated carrier, in 80～120 ℃ of dryings 3～10 hours, in 500～700 ℃ of calcinings 3～15 hours, obtain catalyst intermediate.
12., it is characterized in that the described soluble-salt solution that is selected from strontium, zinc and lanthanum element is strontium nitrate solution, zinc nitrate solution, lanthanum nitrate hexahydrate according to the described preparation method of claim 10, solution concentration is 1～15 (wt) %.
13. the application process of the described load type calcium oxide catalyst of claim 1, comprise: in the presence of load type calcium oxide catalyst, grease is mixed with C1～C5 low-carbon alcohols and carry out ester exchange reaction, separate, collect fatty acid ester of low-carbon alcohol, obtain biodiesel.
14., it is characterized in that described grease is a fatty acid triglyceride according to the described application process of claim 13, wherein the carbon number of aliphatic hydrocarbyl is 6～24, contains 0～5 two key in the aliphatic hydrocarbyl.
15., it is characterized in that described grease is the vegetable fat that is selected from soybean oil, rapeseed oil, peanut oil, sunflower seed oil, palm oil, coconut oil according to the described application process of claim 13.
16., it is characterized in that described low-carbon alcohols is methyl alcohol or ethanol according to the described application process of claim 13.
17., it is characterized in that the mole mixture ratio of grease and low-carbon alcohols is 1: 3～1: 40 according to the described application process of claim 13, the consumption of calcium oxide catalyst is 0.5～20 (wt) % of grease weight, reaction temperature is 0～100.
18. according to claim 13 or 17 described application processes, it is characterized in that the mole mixture ratio of grease and low-carbon alcohols is 1: 6～1: 18, the consumption of calcium oxide catalyst is 1～5 (wt) % of grease weight, reaction temperature is 25～80 ℃, and the reaction time is 0.5-24 hour.
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