CN1986740A - Preparing process for biodiesel oil - Google Patents

Abstract

Translated fromChinese

本发明属于生物柴油制备技术领域。利用高酸值废弃油脂为原料，以树脂为催化剂，通过酯化和酯交换反应得到生物柴油。步骤包括：将酸价为10～105mgKOH/g油的废弃油与低碳醇和阳离子酸性树脂加入反应釜中反应；温度50～100℃，时间3～15h，催化剂含水量1～10％，其与原料油质量百分比17％～50％，油/醇质量体积比1∶0.5～1∶8；离心分离树脂，油相和粗甘油相；油相和粗甘油相分别减压蒸馏出低碳醇，得生物柴油和甘油。与现有技术相比，本发明的催化剂，催化效果好，可再生利用，从而降低生物柴油生产成本，本发明工艺简单，易于工业化，提出的绿色生产工艺，有效地缓解了生物柴油制备过程中对环境的"二次污染"。The invention belongs to the technical field of biodiesel preparation. Using waste oil with high acid value as raw material and resin as catalyst, biodiesel is obtained through esterification and transesterification. The steps include: adding waste oil with an acid value of 10-105mgKOH/g oil, low-carbon alcohol and cationic acidic resin into a reaction kettle for reaction; the temperature is 50-100°C, the time is 3-15h, and the water content of the catalyst is 1-10%. The mass percentage of raw material oil is 17% to 50%, and the oil/alcohol mass volume ratio is 1:0.5 to 1:8; the resin, oil phase and crude glycerin phase are separated by centrifugation; the oil phase and crude glycerin phase are distilled under reduced pressure to obtain low-carbon alcohols respectively, biodiesel and glycerol. Compared with the prior art, the catalyst of the present invention has good catalytic effect and can be recycled, thereby reducing the production cost of biodiesel. The process of the present invention is simple and easy to industrialize. The proposed green production process effectively relieves the production process of biodiesel. "Secondary pollution" to the environment.

Description

The preparation method of bio-diesel oil

Technical field

The invention belongs to technical field of biodiesel preparation.The high acid value waste grease that is specifically related to utilize animal-plant oil tankage, ageing animal-plant oil and catering trade, food-processing industry etc. to produce is the feedstock production method of bio-diesel oil.

Background technology

Animal-plant oil and short chain fatty alcohol are under the effect of catalyzer, and the alkyl esters compound that generates by esterification and transesterification reaction is called biofuel.Biofuel is sulfur-bearing and aromatic hydrocarbons not, the cetane value height, and lubricity is good, is a kind of high-quality clean diesel.In recent years, oil price rises violently and has promoted the development of international biofuel industry, has also caused the attention to biofuel of the Chinese government and some enterprises.Yet stock oil price and competent stock oil supply and new process for cleanly preparing have become the key factor of restriction biofuel development, have only cracked these difficult problems, and China's biofuel industry just is expected to go on the road of extensive industrialized development.Comparatively speaking, high acid value waste greases such as grease processing fent, ageing animal-plant oil, swill oil, sewer oil are not only cheap more than animal-plant oil (referring to crude oil and edible oil), but but also utilization of waste material, environment purification promotes the well-being of mankind.Therefore, it is that stock oil produces thing diesel oil next life that the scientific and technical personnel of units such as some colleges and universities, scientific research institutions or enterprise research and develop one after another in succession with the high acid value waste grease, in the hope of reducing the raw materials cost of biofuel.The existing patent documentation of retrieval, Patent Office of China national Department of Intellectual Property discloses a large amount of relevant with it patents of invention.Disclose the method for utilizing producing biologic diesel oil through obsolete animal and vegetable oils in high acid value as ZL02133591.5, CN1412278A, CN1760336A, CN1861752A, CN1556174, CN1382762A, CN1670128 etc., catalyst system therefor is respectively an acidic catalyst (as the vitriol oil, Phenylsulfonic acid) and caustic soda strong alkali catalyst.Disclose a kind of biological enzyme catalyst high-acid value grease as CN1730613A and carried out transesterification reaction production method of bio-diesel oil; with short-chain aliphatic ester as acyl acceptor; the employing alkaline matter is an additive, utilizes lipase-catalyzed producing biodiesel from high acid number grease.A kind of high acid value animal-plant oil production method of bio-diesel oil of utilizing is disclosed as ZL200310111696.7, catalyzer is mainly strong acid, though related to the macroporous polystyrene storng-acid cation exchange resin in the patent, but must add glycerine in the reaction process, do not provide resin can reuse with and renovation process, technology comprises reaction, washing, winterization, steps such as separation, and it is comparatively loaded down with trivial details to operate.

The non-patent literature report that is the feedstock production biofuel with high acid value grease is also a lot.Inquired into high acid value grease esterification technology as neat Yutang, proposed high acid value oil and can adopt H respectively₂SO₄, NaOH does the esterification of catalyzer substep, emulsion serious (neat Yutang, the research of high acid value oil esterification technology, grain and oil processing and food machinery, 2004 (10): 44-45) are found in experiment.People such as Liu Zhanpeng have then proposed the first step ferric sulfate, second step was made catalyzer with sodium hydroxide, and two-step approach catalysis hogwash fat prepares method of bio-diesel oil (Liu Zhanpeng, the research that two-step approach catalysis hogwash fat prepares biofuel, Chinese oil, 2006 (5): 59-61).People such as Ma Chuanguo have studied sulphuric acid catalysis Oleum Gossypii semen soap stock and have prepared method of bio-diesel oil, having proposed optimum process condition is 60 ℃ of temperature of reaction, reaction times 60min, the ratio of methyl alcohol and lipid acid is 1: 1 (V/W) (Ma Chuanguo, Preparation of biodiesel with soapstock, Chinese oil, 2006 (4): 59-61).People such as Chen Zhifeng have inquired into immobilized lipase Novozym 435 catalysis catering trade peracid waste oil and methyl acetate transesterify production biofuel in the solvent-free system, point out to add organic bases Tutofusin tris or triethylamine, can make the operational stability of enzyme and the catalytic activity (Chen Zhifeng etc. that increase, fixed lipase catalyzed peracid waste oil transesterify production biofuel, the catalysis journal, 2006 (2): 146-150).

In a word, from existing biofuel patent and non-patent literature, we are not difficult to find to exist many technical barriers with the high-acid value grease for the feedstock production biofuel, be mainly reflected in: 1, use base catalysis method production biofuel, owing to there is soap stock to generate in the reaction, form flocks, make the biofuel product not easily separated; The soap stock that generates in the reaction process, glycerine easily and emulsifications such as biofuel, methyl alcohol cause the biofuel yield low; Easy waste discharge forms " secondary pollution " in the reaction; 2, use the vitriol oil to make catalyzer, although have advantages such as catalytic efficiency is higher, the reaction times is short, but same the existence easily discharged sulfuric acid wastewater containing in the reaction, form " secondary pollution ", esterification products is difficult to separate, catalyzer can not be repeated to utilize, thereby causes the more high technical barrier of production cost; 3, use biological enzyme to make catalyzer, though have the reaction conditions gentleness, enzyme catalyst can reuse, do not produce advantages such as waste water, but exist catalytic efficiency not as soda acid two class catalyzer in the reaction, and cause " the glycerine poisoning " of enzyme in the reaction easily, influence the catalytic activity of enzyme, enzyme is short, low to short chain fatty alcohol (as methyl alcohol or ethanol etc.) transformation efficiency in addition work-ing life, and pure consumption is big, cost high-technology defective.

Summary of the invention

The objective of the invention is to overcome the defective that prior art exists, it is succinct to seek a kind of technology, and catalyst is active high, renewable recycling, and production cost is low, the green production technology that in the preparation process environment is not polluted.

For solving the problems of the technologies described above, the present invention has taked following technical scheme:

A kind of preparation method of bio-diesel oil, utilize high acid value waste grease (high acid value waste grease such as trench wet goods that animal-plant oil processing fent, ageing grease, catering trade and food-processing industry etc. produce) to be stock oil, its step comprises: be that stirring down, the acid resin of adding catalyzer positively charged ion carries out esterification and transesterification reaction in the abendoned oil and low-carbon alcohol adding reactor of 10～105mgKOH/g oil with acid value; Temperature of reaction is 50～100 ℃, and the reaction times is 3～15h, and stirring velocity is 300r/min, and described catalyzer water content is 1～10%, and described catalyzer and stock oil mass percent are 17%～50%, and oil/pure mass volume ratio is 1: 0.5～1: 8; The centrifugation of reaction back goes out resin, and oil phase and raw glycerine are mutually; Described catalyzer is through Soxhlet extracting (referring to State Standard of the People's Republic of China GB/T6634-1994 " extraction of crude fat in the feed ", China Standard Press, 1995) regeneration recycling of deoiling; With described oil phase and raw glycerine mutually respectively underpressure distillation go out methyl alcohol, obtain biofuel and glycerine.

Described preparation method of bio-diesel oil is characterized in that, described acidic resins are selected from a kind of of polystyrene resin cation (R.C.) or cinnamic acid cation resin.

Described preparation method of bio-diesel oil is characterized in that, the required reagent of esterification and transesterification reaction is low-carbon alcohol, and this low-carbon alcohol is selected from methyl alcohol, ethanol, propyl alcohol or butanols a kind of.

Described preparation method of bio-diesel oil, it is characterized in that, esterification and transesterification reaction temperature are 60～80 ℃, reaction times is 3～8h, catalyzer water content 1～4%, described catalyzer and stock oil mass percent are 18%～40%, and described oil/pure mass volume ratio is 1: 0.7～1: 5.

Described preparation method of bio-diesel oil is characterized in that, described catalyzer water content is 1～2%, and oil/pure mass volume ratio is 1: 0.7～1: 2.

Described preparation method of bio-diesel oil is characterized in that, the pressure of underpressure distillation is 0.1MPa, and temperature is 65 ℃.

Described preparation method of bio-diesel oil is characterized in that, the regeneration of described catalyzer is to use anhydrous diethyl ether as extraction agent, and its consumption is 4～10 times of described catalyst quality, and drying temperature is 105 ℃, and be 1h time of drying.

Compared with prior art, positively effect of the present invention is:

1, the acid resin catalyst of the positively charged ion of the present invention's employing prepares biofuel, compare with existing concentrated sulfuric acid catalyst, and the catalytic activity height, the biofuel transformation efficiency is up to 98.1%.

2, prepare biofuel with classical acid or base catalysis and compare, the catalyzer that the present invention adopts can be regenerated and can be recycled, and uses 4～5 artifact diesel oil transformation efficiencys still more than 94% repeatedly.

3, the biodiesel of the present invention's employing, its technical process is succinct, aftertreatment need not the neutralization washing can obtain products such as biofuel and glycerine, be easy to realize suitability for industrialized production, the reaction conditions gentleness, applied widely, not being only applicable to the high acid value waste grease is the feedstock production biofuel, but also applicable to being the feedstock production biofuel with natural animal-plant oil.The entire production process without sewage discharge belongs to the green production process technology.

Description of drawings

Fig. 1 is technological line figure of the present invention.

Fig. 2 is that catalyst regeneration of the present invention utilizes process flow sheet.

Fig. 3 is four kinds of different catalysts testing of the present invention to the catalytic effect of high-acid-value material oil relatively.Among the figure: CHJ01, CHJ02 are macropore strong acid polystyrene resin cation (R.C.); CHJ03, CHJ04 are macroreticular acidic cinnamic acid cation resin.

Fig. 4 is that one of them is numbered in the CHJ01 catalyzer moisture content to the influence of biofuel transformation efficiency among the present invention.

Embodiment

In following embodiment, described stock oil all carries out pre-treatment according to the document treatment process of the above-mentioned report of this specification sheets.

Embodiment 1:

Raw material: get pretreated sewer oil 100g, the acid value of measuring stock oil is a 20mgKOH/g oil.

At first, the 250mL there-necked flask is put into thermostat water bath, and on there-necked flask, load onto reflux condensing tube successively, electric mixer and thermometer.Add 100g through pretreated sewer oil and 150mL dehydrated alcohol in the past then there-necked flask, adding 30g moisture content is 1.5% large hole strong acid styrene system cation exchange resin (CHJ01) under stirring.Heating in water bath to 70 ℃ is opened electric mixer, and stirring velocity is 300r/min, and stirring reaction is after 5 hours, and suction filtration gets resin and oil phase.With 25mL absolute ethanol washing resin 3 times, washings is integrated with in the oil phase.Resin is removed in the resin and is not washed most grease as yet with 180mL anhydrous diethyl ether Soxhlet extracting 2.h.To reclaim resin after extracting stops and putting into 105 ℃ of thermostatic drying chambers and activate 1h, insert in the drying basin in order to recycling.At last oil phase is inserted under 0.1MPa and the 65 ℃ of conditions underpressure distillation and reclaims ethanol, the 86g biofuel, the biofuel transformation efficiency is 98.1%.Under the constant situation of above-mentioned experimental raw, compared the effect that traditional sulphuric acid catalysis legal system is equipped with resin CHJ01 catalytic method for preparing biological diesel oil among biofuel and the present invention, see Table 1.

The effect of table 1 sulfuric acid catalysis method and resin CHJ01 catalytic method for preparing biological diesel oil of the present invention relatively

Reaction conditions	Sulphuric acid catalysis method (CK)	Resin CHJ01 catalysis method of the present invention
			Raw material and consumption/g	Pretreated sewer oil 100g	Pretreated sewer oil 100g
Oil/pure mass volume ratio catalyst amount/% catalyst reuse the situation reaction temperature/℃ reaction time/h separation of products situation product appearance biodiesel conversion ratio/% sewage discharge situation	Can not the sulfuric acid wastewater containing discharging be arranged 65 2.5 difficult black 97.2 in 1: 0.8 5	Reused repeatedly 70 5 easy reddish brown 98.1 without sewage discharges in 1: 1.5 30

Embodiment 2:

Raw material: soybean oil tankage 100g, the acid value of measuring stock oil is a 85mgKOH/g oil.

At first, the 250mL there-necked flask is put into thermostat water bath, and on there-necked flask, load onto reflux condensing tube successively, electric mixer and thermometer.Add 100g soybean oil tankage and 70mL anhydrous methanol in the past then there-necked flask, adding 18g moisture content is 1% large hole strong acid styrene system cation exchange resin (CHJ01) under stirring.Heating in water bath to 60 ℃ is opened electric mixer, and stirring velocity is 300r/min, and stirring reaction is after 3 hours, and suction filtration gets resin and oil phase.With 12mL methanol wash resin 3 times, washings is integrated with in the oil phase.Resin is removed in the resin and is not washed most grease as yet with 68mL anhydrous diethyl ether Soxhlet extracting 2h.To reclaim resin after extracting stops and putting into 105 ℃ of thermostatic drying chambers and activate 1h, insert in the drying basin in order to recycling.At last oil phase is inserted under 0.1MPa and the 65 ℃ of conditions underpressure distillation and reclaims methyl alcohol, the 83g biofuel, the biofuel transformation efficiency is 95.9%.

Embodiment 3:

Raw material: ageing rapeseed oil 100g, the acid value of measuring stock oil is a 105mgKOH/g oil.

At first, the 250mL there-necked flask is put into thermostat water bath, and on there-necked flask, load onto reflux condensing tube successively, electric mixer and thermometer.Add rotten rapeseed oil of 100g and 200mL anhydrous methanol then in the there-necked flask, stir that to add the 40g moisture content down respectively be 2% macropore strong acid vinylbenzene Zeo-karb (CHJ01).Heating in water bath to 80 ℃ is opened electric mixer, and stirring velocity is 300r/min, and stirring reaction is after 8 hours, and suction filtration gets resin and oil phase.With 40mL methanol wash resin, washings is incorporated in the oil phase.Resin is removed in the resin and is not washed most grease as yet with 400mL anhydrous diethyl ether Soxhlet extracting 2h.To reclaim resin after extracting stops and putting into 105 ℃ of thermostatic drying chambers and activate 1h, insert in the drying basin in order to recycling.At last methyl alcohol is reclaimed in oil phase underpressure distillation under 0.1MPa, get the 84g biofuel, the biofuel transformation efficiency is 97.1%.

Repeat above-mentioned experiment, other conditions are constant, just change the original situation of catalyzer, and promptly add 40g respectively and reused 2 times, 3 times, 4 times and 5 macropore strong acid vinylbenzene Zeo-karb CHJ01.After reaction finishes, calculate the biofuel transformation efficiency, the results are shown in Table 2.

Table 2 resin CHJ01 recycling of the present invention number of times is to the influence of biofuel transformation efficiency

The repeated use number of times/time	1	2	3	4	5
						Biofuel rate/%	97.1	95.7	95.3	94.6	94.1

Embodiment 4:

Raw material: frying oil 100g, the acid value of measuring stock oil is a 30mgKOH/g oil.

Step according to embodiment 1 is poly-, changes dehydrated alcohol into anhydrous propyl alcohol, and the consumption of anhydrous propyl alcohol is 150mL, and adding 30g moisture content is 1.5% macropore cinnamic acid cation exchange resin (CHJ03) under stirring, and other steps are constant.Get the 82g biofuel after reaction finishes, the biofuel transformation efficiency is 85.6%.

Embodiment 5:

Raw material: natural rapeseed oil 100g, the acid value of measuring stock oil is a 1.8mgKOH/g oil.

Step according to embodiment 1 is poly-, changes dehydrated alcohol into anhydrous methanol, and the consumption of anhydrous methanol is 80mL, and other steps and condition are constant.Get the 88g biofuel after reaction finishes, the biofuel transformation efficiency is 97.8%.

Embodiment 6:

Raw material: crude soya bean oil 100g, the acid value of measuring stock oil is a 2.0mgKOH/g oil.

Step according to embodiment 1 is poly-, changes dehydrated alcohol into butanols, and the consumption of butanols is 120mL, and other steps and condition are constant.Get the 87g biofuel after reaction finishes, the biofuel transformation efficiency is 97.2%.

Embodiment 7:

Raw material: lard 100g, the acid value of measuring stock oil is a 1.7mgKOH/g oil.

Step according to embodiment 1 is poly-, changes dehydrated alcohol into methyl alcohol, and the consumption of methyl alcohol is 100mL, and other steps and condition are constant.Get the 84g biofuel after reaction finishes, the biofuel transformation efficiency is 97.4%.

Embodiment 1～7 experimental result aggregation sees Table 3.

The experimental result of table 3 resin CHJ01 catalytic method for preparing biological diesel oil

Experimental raw	Stock oil acid value/mgKOH/g oil	Biofuel transformation efficiency/%
			Waste oil soybean oil leftover bits and pieces aged rapeseed oil frying oil rapeseed oil soybean oil lard	20 85 105 30 1.8 2.0 1.7	98.1 95.9 97.1 85.6 97.8 97.2 97.4

Claims (7)

Translated fromChinese

1、一种制备生物柴油的方法，利用高酸值废弃油脂为原料油，其步骤包括：将酸价为10～105mgKOH/g油的废弃油与低碳醇加入反应釜中，搅拌下加入催化剂阳离子酸性树脂进行酯化和酯交换反应；反应温度为50～100℃，反应时间为3～15h，搅拌速度为300r/min，所述的催化剂含水量为1～10％，所述的催化剂与原料油质量百分比为17％～50％，油/醇质量体积比为1∶0.5～1∶8；反应后离心分离出树脂，油相和粗甘油相；所述的催化剂经索氏抽提去油再生重复利用；将所述的油相和粗甘油相分别减压蒸馏出甲醇，得到生物柴油和甘油。1. A method for preparing biodiesel, using waste oil with high acid value as raw material oil, the steps include: adding waste oil with an acid value of 10 to 105 mgKOH/g oil and low-carbon alcohol into a reactor, and adding a catalyst under stirring The cationic acidic resin is subjected to esterification and transesterification; the reaction temperature is 50-100°C, the reaction time is 3-15h, the stirring speed is 300r/min, the water content of the catalyst is 1-10%, and the catalyst and The mass percentage of the raw material oil is 17% to 50%, and the oil/alcohol mass volume ratio is 1:0.5 to 1:8; after the reaction, the resin, oil phase and crude glycerin phase are separated by centrifugation; the catalyst is removed by Soxhlet extraction. The oil is regenerated and reused; the oil phase and the crude glycerin phase are respectively distilled out of methanol under reduced pressure to obtain biodiesel and glycerin.2、根据权利要求1所述的制备生物柴油的方法，其特征在于，所述的酸性树脂选自苯乙烯系阳离子树脂或苯丙烯酸系阳离子树脂之一种。2. The method for preparing biodiesel according to claim 1, wherein the acidic resin is selected from one of styrene-based cationic resins and phenylacrylic-based cationic resins.3、根据权利要求1或2所述的制备生物柴油的方法，其特征在于，酯化和酯交换反应所需试剂为低碳醇，该低碳醇选自甲醇，乙醇，丙醇或丁醇之一种。3. The method for preparing biodiesel according to claim 1 or 2, characterized in that the reagents required for esterification and transesterification are low-carbon alcohols, and the low-carbon alcohols are selected from methanol, ethanol, propanol or butanol one of a kind.4、根据权利要求1、2或3所述的制备生物柴油的方法，其特征在于，酯化和酯交换反应温度为60～80℃，反应时间为3～8h，催化剂含水量1～4％，所述的催化剂与原料油质量百分比为18％～40％，所述的油/醇质量体积比为1∶0.7～1∶5。4. The method for preparing biodiesel according to claim 1, 2 or 3, characterized in that the reaction temperature of esterification and transesterification is 60-80°C, the reaction time is 3-8 hours, and the water content of the catalyst is 1-4%. , the mass percentage of the catalyst and the raw oil is 18%-40%, and the mass volume ratio of the oil/alcohol is 1:0.7-1:5.5、根据权利要求4所述的制备生物柴油的方法，其特征在于，所述的催化剂含水量为1～2％，油/醇质量体积比为1∶0.7～1∶2。5. The method for preparing biodiesel according to claim 4, characterized in that the water content of the catalyst is 1-2%, and the mass volume ratio of oil/alcohol is 1:0.7-1:2.6、根据权利要求1所述的制备生物柴油的方法，其特征在于，减压蒸馏的压力为0.1MPa，温度为65℃。6. The method for preparing biodiesel according to claim 1, characterized in that the pressure of vacuum distillation is 0.1 MPa, and the temperature is 65°C.7、根据权利要求1所述的制备生物柴油的方法，其特征在于，所述催化剂的再生利用是用无水乙醚为抽提试剂，其用量为所述催化剂质量的4～10倍，干燥温度为105℃，干燥时间为1h。7. The method for preparing biodiesel according to claim 1, characterized in that, the recycling of the catalyst is to use anhydrous diethyl ether as the extraction reagent, the amount of which is 4 to 10 times the mass of the catalyst, and the drying temperature The temperature is 105°C, and the drying time is 1h.

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