CN110343573A - A kind of method of modifying of grease and its application - Google Patents
A kind of method of modifying of grease and its application Download PDFInfo
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- CN110343573A CN110343573A CN201910482549.1A CN201910482549A CN110343573A CN 110343573 A CN110343573 A CN 110343573A CN 201910482549 A CN201910482549 A CN 201910482549A CN 110343573 A CN110343573 A CN 110343573A
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- grease
- ozonisation
- waste oil
- fertilizer
- heat treatment
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B17/00—Other phosphatic fertilisers, e.g. soft rock phosphates, bone meal
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/10—Solid or semi-solid fertilisers, e.g. powders
- C05G5/12—Granules or flakes
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/30—Layered or coated, e.g. dust-preventing coatings
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/006—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by oxidation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- General Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Fertilizers (AREA)
Abstract
The invention discloses a kind of method of modifying of grease and its applications.This method comprises the following steps: 1) being modified using ozone to the grease, obtain ozonisation grease；2) ozonisation grease is modified again under heating conditions, ozonisation grease must be heat-treated.The present invention is modified grease using ozone and heating, oil modification material only can be prepared by by two-step reaction, thus this method is simple, efficiently, it is easy to accomplish, and this method solve the simple problems for being modified occur unstable to grease using ozone and coating effect is poor.This method without using any solvent and other additives, meanwhile, be modified using waste oil, catabolite be nutrient for plants.This method heat treatment ozonisation grease obtained, stability is good, and hydrophobicity is strong, is applied in coat fertilizer, and obtained coat fertilizer initial stage nutrient release amount interior for 24 hours meets the standard of the coated fertilizer of coat fertilizer less than 15%.
Description
Technical field
The present invention relates to the method for modifying and its application of technical field of material modification more particularly to a kind of grease.
Background technique
Chemical fertilizer is grain " grain ", can promote grain growth, but chemical fertilizer is excessively used to bring a series of negative influences,
Such as the wasting of resources, environmental disruption, contaminated drinking water etc..And coat fertilizer can avoid chemical fertilizer and directly contact with the external world, reduce chemical fertilizer waste,
Chemical fertilizer utilization ratio is improved, extends fertilizer efficiency and is therefore concerned.Currently, the consumption of the annual nitrogenous fertilizer in the whole world, phosphate fertilizer, potash fertilizer is total
About 110,000,000 tons of amount, and coat fertilizer consumption is less than 500,000 tons[1].Although have several commodity coat fertilizers makes in agricultural
With, but dosage is limited, main reason is that its cost is excessively high, it is 2~6 times of general fertilizers[2], and preparation process is complicated[3], resistance
Extensive use of the coat fertilizer in agricultural is hindered.
Waste grease includes industrial waste oil and waste cooking oil, and people's concern is more waste cooking oil, it is also known as " useless
Oil ", " hogwash fat ", " gutter oil " etc..China is a populous nation, and the consumption of materials is huge, generates about 8,000,000 tons of food and drink every year
Waste oil[4].Dealing with improperly for waste oil generates a series of negative influences, on the one hand, waste oil direct emission polluted-water, frozen plug
Sewer causes municipal sewage to overflow, and destroys city image, and on the other hand, waste grease is illegally processed, and does not remove nuisance
Matter, the dining table that flows back can destroy human physiological functions, cause adverse effect to human health after people is edible.In recent years, people
Biodiesel, but complex process mostly are prepared by raw material of waste oil, it is at high cost, fail to promote and apply.
Currently, having research and utilization waste oil is that raw material prepares coat fertilizer, waste oil outlet is solved, realizes that waste oil circulation, height are additional
Value utilizes.CN108558515A is disclosed using diethylene glycol, glycerine, 1,4- butanediol, 1,6-HD, ethylene glycol and is gathered
The mixture of one or more of ethylene glycol is gutter oil modifying agent, and one or more of sulfuric acid, hydrochloric acid or phosphoric acid are to urge
Agent, paraphenylene diisocyanate, polymethylene multi-phenenyl isocyanate, dimethyl diphenyl diisocyanate, diphenyl methane two
The mixture of one or more of isocyanates or trimethyl hexamethylene diisocyanate is curing agent, it is glued with nanometer
Soil, which is uniformly mixed, sprays to fertiliser granulates surface reaction film forming as coated fertilizer, prepares release-controlled coated fertilizer；CN103755866A
It disclosing using gutter oil as raw material, the reactions such as addition crylic acid hydroxy ester, polymerization inhibitor, crosslinking agent and catalyst obtain prepolymer,
Granulated fertilizer surface is sprayed to, obtains coat fertilizer after being heating and curing；Liu little Qi[5]Using frying waste oil in hydroxyl can with it is different
Polyisocyanate reactant makes it in urea surface film-forming, obtains coat fertilizer.Although the renewable of waste oil can be achieved in the studies above
It utilizes, but has that more additive, complex process, complex steps, modified higher cost, etc. unfriendly to environment are a series of to ask
Topic.
Using grease as carrier, ozone is that ozonisation grease can be made in reactant, but ozonizes residue ozone in grease, a side
Face ozone is extremely unstable at normal temperatures and pressures, can be analyzed to oxygen[6]；On the other hand, in placement process, residue ozone causes
Ozonization will continue to carry out；Furthermore ozonisation grease can also decompose in long-time placement process, lead to ozone carburetion
Rouge stability is poor.
Thus, how to overcome the series of problems after being modified using ozone to grease, makes it have better stability
And better coating effect, however it remains certain challenge.
Bibliography:
[1] Li Meiqing organic matter and inorganic mineral be to comparative study [D] the Agricultural University Of Shanxi of nitrogen slowly releasing effect,
2004.
[2] Tan Jinfang, the dawn that is situated between is of heap of stone, changes the whole county, Yu Changkun, Wang Yilun, the production of Ma Weidong inorganic coating slowly/controlled releasing fertilizer
Technique and fertilizer efficiency inquire into [J] Agricultural University Of He'nan journal, 2003 (03): 257-262.
[3] Liu Junjie slow-release nitrogen fertilizer-poly- carbonyl urea synthesising process research [D] Northcentral University, 2013.
[4] biology boat coal: the Silicon Valley aircraft industry emission reduction counterweight [J], 2014,7 (05): 11.
[5] Shandong research [D] of the preparation of Liu little Qi plant oil base coated release-controlled urea and its controlled release properties agricultural is big
It learns, 2017.
[6] preparation of Yang Ye ozone carburetion and its control efficiency research [D] the Agricultural University Of Hebei to apple tree canker,
2014.
Summary of the invention
The purpose of the present invention is to provide a kind of method of modifying of grease and its applications.The present invention passes through to ozonisation grease
Further heating reaction is carried out, can solve the problem that ozone is modified rear stability difference to grease, meanwhile, further heat
Reaction can also improve the hydrophobicity of product, have better coating effect.
Specifically:
One of the objects of the present invention is to provide a kind of method of modifying of grease, include the following steps:
1) grease is modified using ozone, obtains ozonisation grease；
2) ozonisation grease is modified again under heating conditions, ozonisation grease must be heat-treated.
Preferably, above-mentioned grease can be edible oil, or waste grease.
Preferably, above-mentioned grease is the grease containing C=C functional group.
It is worth noting that: the grease of the invention containing C=C functional group can be arbitrary grease, such as single animal
Oil or vegetable oil or its mixing, vegetable oil include peanut oil, rapeseed oil, soya-bean oil, castor oil, linseed oil, rice bran oil, corn oil,
Olive oil, tung oil etc.；Animal oil includes lard, butter, sheep oil, fish oil etc..
Preferably, if it is necessary, further including being heated under vacuum conditions to above-mentioned grease to remove excessive water
The step of dividing, so that the mass fraction in grease containing water is no more than 5%.
Preferably；Above-mentioned grease is selected from waste grease.
It preferably, if necessary, further include that pre-treatment is carried out to waste grease, except shakeout, stone, branch, dish, rice grain etc.
Solid particle polluter, or the step of heating under vacuum conditions to remove excessive moisture, so that the water that waste grease contains
Mass fraction is no more than 5%.
Preferably, the volume ratio of step 1) ozone flow and above-mentioned grease is 0.15~1g/mL, and the time that ozone is passed through is
2~14h.
It is highly preferred that the volume ratio of ozone flow and above-mentioned grease in step 1) is 0.25~0.625g/mL, ozone is logical
The time entered is 5~10h.
Preferably, ozone is 10~40 DEG C to the temperature that grease is modified in step 1)；More preferably 15~30 DEG C.
Preferably, the heating temperature of step 2) is 60~120 DEG C, and heating time is 6~30h.
It is highly preferred that the heating temperature of step 2) is 80~120 DEG C, heating time is 8~20h.
Another object of the present invention is to provide the heat treatments that the above method is prepared to ozonize grease as coating material
The application of material.
Preferably, above-mentioned heat treatment ozonisation grease is used to prepare coat fertilizer as coated fertilizer.
The present invention also provides a kind of coat fertilizers, including fertilizer and positioned at the coated fertilizer of fertilizer outer layer, above-mentioned packet
Membrane material includes that heat treatment prepared by the above method ozonizes grease.
Preferably, the outer layer of above-mentioned coat fertilizer includes multiple by the heat treatment layers that form of ozonisation grease and positioned at interlayer
Reinforce substance.
Preferably, above-mentioned stiffener is of fine quality is selected as sulphur powder, biogas residue powder, phosphate, silicate, charcoal, straw powder, bamboo
At least one of charcoal, mineral powder, zeolite powder, bentonite highly surface activated mineral, composition silicate.
Preferably, total nutrient (N+P in above-mentioned coat fertilizer2O5+K2O mass fraction) is 30% or more.
Preferably, above-mentioned heat treatment ozonizes grease: fertilizer: the mass ratio for reinforcing substance is (0.4~1.2): 10:(3.3
~4.1).
It is highly preferred that above-mentioned heat treatment ozonizes grease: fertilizer: the mass ratio for reinforcing substance is (0.5~1): 10:(3.4
~4.0).
Preferably, above-mentioned fertilizer is selected from least one of nitrogenous fertilizer, phosphate fertilizer, potash fertilizer or trace-element fertilizer, such as: urine
Element, ammonium hydrogen carbonate, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium chloride, potassium nitrate etc..
Preferably, above-mentioned fertilizer is the form of particle.
Preferably, the partial size of above-mentioned particle is 1.5~4.75mm.
It is highly preferred that the partial size of above-mentioned particle is 2~4.75mm.
Preferably, above-mentioned coat fertilizer can be prepared via a method which to obtain:
Heat treatment ozonisation grease is adhered to fertiliser granulates surface, so that fertilizer of the heat treatment ozonisation grease in movement
Particle surface is coated, and coat fertilizer is obtained.
It is highly preferred that above-mentioned coat fertilizer is made by the steps to obtain:
1) heat treatment ozonisation grease is attached into fertiliser granulates surface, makes heat treatment ozonisation grease in the fertilizer of movement
Particle surface is coated；
2) it is added and reinforces substance, so that it is uniformly wrapped on heat treatment ozonisation grease surface, form first layer reinforcing layer；
3) it repeats step 1) and it 2), is made to form single-layer or multi-layer reinforcing layer in the outer layer of coat fertilizer, obtain coat fertilizer.
Preferably, above-mentioned reinforcing substance is selected from sulphur powder, biogas residue powder, phosphate, silicate, charcoal, straw powder, bamboo
At least one of charcoal, mineral powder, zeolite powder, bentonite highly surface activated mineral, composition silicate.
Preferably, the partial size of above-mentioned reinforcing substance is 80~300 mesh；More preferably 80~150 mesh.
The beneficial effects of the present invention are:
1, the present invention is modified grease using ozone and heating, only can be prepared by oil modification material by two-step reaction
Material, thus this method is simple, efficient, it is easy to accomplish, and this method solve be modified appearance to grease using ozone merely
The storage of unstable and coat fertilizer too long bad stability the problem of.
2, this method is without using any solvent and other additives, meanwhile, it is modified using waste oil, catabolite
It is small for nutrient for plants and ozone usage, and ozone is cleaning renewable resource, which is not necessarily to use expensive set
Standby and equipment uses less, therefore is conducive to cost control and not will cause new environmental pollution, is suitable for extensive environmentally protective life
It produces.
3, this method heat treatment ozonisation grease obtained, stability is good, and hydrophobicity is strong, is applied in coat fertilizer,
Obtained coat fertilizer initial stage nutrient release amount interior for 24 hours meets the standard of the coated fertilizer of coat fertilizer less than 15%.
Detailed description of the invention
Fig. 1 is that ozonisation waste oil prepared by embodiment 1 and the FTIR of heat treatment ozonisation waste oil scheme；
Fig. 2 is the pictorial diagram of coat fertilizer prepared by embodiment 23；
Fig. 3 is the film layer of coat fertilizer prepared by embodiment 23 and the FTIR of heat treatment ozonisation waste oil and ground phosphate rock used
Figure；
Fig. 4: a schemes (× 1000) for the surface SEM of 23 coat fertilizer of embodiment；B is that the section SEM of 23 coat fertilizer of embodiment schemes
(×2000)；
Fig. 5 is the different heat treatment time in Examples 1 to 6 to the influence diagram of product contact angle:
Fig. 6 is the different heat treatment time in Examples 1 to 6 to the influence diagram of product acid value；
Fig. 7 is the standard curve of urea release.
Specific embodiment
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art are according to the present invention
Some nonessential modifications and adaptations that the principle of elaboration is made all belong to the scope of protection of the present invention.Following specific works of example
Skill parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this patent
Selection in range, and do not really want to be defined in hereafter exemplary specific data.
Test raw material and reagent:
1, waste grease (waste oil): for soybean waste oil, acid value is 40~50mgKOH/g；
2, potassium hydroxide: Tianjin Fu Yu Fine Chemical Co., Ltd；
3, Sodium Thio Sulphate(Anhydrous), potassium iodide: Tianjin good fortune morning chemical reagent factory；
4, potassium bichromate, the concentrated sulfuric acid, concentrated hydrochloric acid: Tianjin all generations Chemical Co., Ltd.；
5, soluble starch: Xilong Chemical Co., Ltd；
6, paradime thylaminobenzaldehyde: the new fine chemistry industry development centre in Tianjin day；
Mentioned reagent is that analysis is pure.
Test apparatus:
1, HY-005-10A ozone machine: Guangzhou Jia Huan electric appliance Science and Technology Ltd.；
2,101-1AB type electric drying oven with forced convection: Tianjin Stettlen Instrument Ltd.；
3, FTIR:PS15 type Fourier infrared spectrograph；
4, UV-1800 ultra-violet and visible spectrophotometer: Japanese Shimadzu Corporation；
5, EVO18 type scanning electron microscope: German Zeiss company；
6, contact angle: Sweden's Biolin Scientific Theta optical contact angle measuring instrument.
Test method:
Waste grease, which is ozonized, contains a large amount of peroxide in modified obtained ozonisation waste oil, peroxide heat
Stability is poor, and heating makes its decomposition, obtains small molecule acid, polymerization reaction, which occurs, for these small molecule acid and fatty acid can make system
Middle free acid is reduced, and acid value is caused to decline, therefore acid value is the main indicator of heat treatment ozonisation waste oil modification degree；Using connecing
Feeler tests the hydrophobicity of heat treatment ozonisation waste oil, and contact angle is bigger, and hydrophobicity is stronger, and contact angle is smaller, hydrophilic
Property is stronger,；With the functional group of the film layer of infrared test ozonisation waste oil, heat treatment ozonisation waste oil, ground phosphate rock and coat fertilizer, divide
Analysing the coat fertilizer prepared by it has the reason of slow release effect, and concrete operations are as follows:
1, acid value: referring to the measurement of hot ethanol indicator titration method, following embodiments or comparison in GB 5009.229-2016
Such as without special instruction, the acid value for ozonizing waste oil is tested after freshly prepd ozonisation waste oil is placed 5 days, is heat-treated
Ozonisation waste oil acid value without place directly tested obtained by.
2, infrared: infrared scan, resolution ratio 4cm are carried out using KBr smear method-1, scan accumulative frequency 4 times；
3, contact angle: exploratory experiment is shown: if grease is applied directly on sheet glass, water droplet is rolled, and is not fixed, can not
Accurate Determining contact angle, filter paper are that carrier can solve this problem.Meanwhile appropriate heating exists after smearing grease conducive to grease
Evenly dispersed on filter paper, particularly with the biggish oil sample of viscosity, directly smearing uniformity is poor, does not heat, water can be directly saturating
Filter paper, the result cannot reflect that the true hydrophobicity of grease is comparable to reach test effect also for test,
80 DEG C of heating 30min after the unified smearing of this test, take the average value in 10s.
Concrete operations are as follows: be uniformly applied to sample to be tested on the filter paper of 7 × 10mm, 80 DEG C of heating 30min obtain oil
Ultrapure water is added dropwise on oil film using injection needle for film, tests the contact angle of the oil film and water.
Test display: since freshly prepd ozonisation waste oil is unstable, contact angle constantly reduces in placement process, but puts
It after setting 5 days, tends towards stability, therefore the contact angle of following ozonisation waste oil is surveyed after placing 5 days unless otherwise instructed
Examination gained, in addition, following embodiments are to place 5 using freshly prepd ozonisation waste oil unless otherwise instructed for convenient for comparison
It carries out heat treatment preparation heat treatment ozonisation waste oil again, and the contact angle for being heat-treated ozonisation waste oil is directly contacted
Angle test, without placing.
Embodiment 1
A kind of oil modification method, includes the following steps:
1) preparation of waste oil is ozonized:
Taking 80mL waste oil, (acid value 46.45mgKOH/g, the mass fraction of water use under the conditions of 20~30 DEG C less than 5%)
Air source ozone machine is continually fed into ozone 5h with the flow of 10g/h, obtains ozonisation waste oil；
2) preparation of heat treatment ozonisation waste oil:
Ozonisation waste oil is heated into 12h under the conditions of 120 DEG C, ozonisation waste oil must be heat-treated.
To understand fully influence of the heating to ozonisation waste oil structure, ozonisation waste oil and heat treatment ozonisation waste oil are carried out red
Outer comparison, as a result as shown in Figure 1.As shown in Figure 1: ozonisation waste oil is in 3450cm-1And 2925cm-1There are wider absorptions at place
Peak, heat treatment ozonisation waste oil this at two absorption peak weaken；1632cm-1And 1745cm-1Place is that the stretching vibration of C=O is inhaled
Peak is received, heat treatment ozonisation waste oil is in 1632cm-1Locate characteristic absorption peak to disappear, 1745cm-1Place's characteristic absorption peak narrows, this table
Bright ozonisation waste oil is heated modified, and carboxyl is reduced, and acid value reduces.
Embodiment 2~6
The preparation method of embodiment 2~6 is same as Example 1, the difference is that: embodiment 2~6 is right in step 2)
Ozonisation waste oil heating time be respectively 0h, for 24 hours, 36h, 48h, 60h.
Embodiment 7
A kind of method of modifying of grease, includes the following steps:
1) preparation of waste oil is ozonized:
Taking 80mL waste oil, (acid value 46.45mgKOH/g, the mass fraction of water use air less than 5%) under the conditions of 15 DEG C
Source ozone machine is continually fed into ozone 5h with the flow of 2.4g/h, obtains ozonisation waste oil；
2) preparation of heat treatment ozonisation waste oil:
Ozonisation waste oil is heated into 6h under the conditions of 120 DEG C, ozonisation waste oil must be heat-treated.
Embodiment 8
A kind of method of modifying of grease, includes the following steps:
1) preparation of waste oil is ozonized:
Taking 80mL waste oil, (acid value 46.45mgKOH/g, the mass fraction of water use air less than 5%) under the conditions of 15 DEG C
Source ozone machine is continually fed into ozone 5h with the flow of 16g/h, obtains ozonisation waste oil；
2) preparation of heat treatment ozonisation waste oil:
Ozonisation waste oil is heated into 6h under the conditions of 60 DEG C, ozonisation waste oil must be heat-treated.
Embodiment 9
A kind of method of modifying of grease, includes the following steps:
1) preparation of waste oil is ozonized:
Taking 80mL waste oil, (acid value 46.45mgKOH/g, the mass fraction of water use air less than 5%) under the conditions of 15 DEG C
Source ozone machine is continually fed into ozone 5h with the flow of 4g/h, obtains ozonisation waste oil；
2) preparation of heat treatment ozonisation waste oil:
Ozonisation waste oil is heated into 15h under the conditions of 120 DEG C, ozonisation waste oil must be heat-treated.
Embodiment 10
A kind of method of modifying of grease, includes the following steps:
1) preparation of waste oil is ozonized:
Taking 80mL waste oil, (acid value 46.45mgKOH/g, the mass fraction of water use air less than 5%) under the conditions of 15 DEG C
Source ozone machine is continually fed into ozone 5h with the flow of 3g/h, obtains ozonisation waste oil；
2) preparation of heat treatment ozonisation waste oil:
Ozonisation waste oil is heated into 20h under the conditions of 120 DEG C, ozonisation waste oil must be heat-treated.
Embodiment 11
A kind of method of modifying of grease, includes the following steps:
1) preparation of waste oil is ozonized:
Taking 80mL waste oil, (acid value 46.45mgKOH/g, the mass fraction of water use air less than 5%) under the conditions of 15 DEG C
Source ozone machine is continually fed into ozone 2.5h with the flow of 16g/h, obtains ozonisation waste oil；
2) preparation of heat treatment ozonisation waste oil:
Ozonisation waste oil is heated into 8h under the conditions of 90 DEG C, ozonisation waste oil must be heat-treated.
Embodiment 12
A kind of method of modifying of grease, includes the following steps:
1) preparation of waste oil is ozonized:
Taking 80mL waste oil, (acid value 46.45mgKOH/g, the mass fraction of water use air less than 5%) under the conditions of 15 DEG C
Source ozone machine is continually fed into ozone 10h with the flow of 2.4g/h, obtains ozonisation waste oil；
2) preparation of heat treatment ozonisation waste oil:
Ozonisation waste oil is heated into 8h under the conditions of 80 DEG C, ozonisation waste oil must be heat-treated.
Embodiment 13
A kind of method of modifying of grease, includes the following steps:
1) preparation of waste oil is ozonized:
Taking 80mL waste oil, (acid value 46.45mgKOH/g, the mass fraction of water use air less than 5%) under the conditions of 15 DEG C
Source ozone machine is continually fed into ozone 14h with the flow of 2.4g/h, obtains ozonisation waste oil；
2) preparation of heat treatment ozonisation waste oil:
Ozonisation waste oil is heated into 8h under the conditions of 80 DEG C, ozonisation waste oil must be heat-treated.
Embodiment 14
A kind of method of modifying of grease, includes the following steps:
1) preparation of waste oil is ozonized:
Taking 80mL waste oil, (acid value 46.45mgKOH/g, the mass fraction of water use air less than 5%) under the conditions of 10 DEG C
Source ozone machine is continually fed into ozone 5h with the flow of 8g/h, obtains ozonisation waste oil；
2) preparation of heat treatment ozonisation waste oil:
Ozonisation waste oil is heated into 8h under the conditions of 80 DEG C, ozonisation waste oil must be heat-treated.
Embodiment 15
A kind of method of modifying of grease, includes the following steps:
1) preparation of waste oil is ozonized:
Taking 80mL waste oil, (acid value 46.45mgKOH/g, the mass fraction of water use air less than 5%) under the conditions of 30 DEG C
Source ozone machine is continually fed into ozone 5h with the flow of 8g/h, obtains ozonisation waste oil；
2) preparation of heat treatment ozonisation waste oil:
Ozonisation waste oil is heated into 10h under the conditions of 70 DEG C, ozonisation waste oil must be heat-treated.
Embodiment 16
A kind of method of modifying of grease, includes the following steps:
1) preparation of waste oil is ozonized:
Taking 80mL waste oil, (acid value 46.45mgKOH/g, the mass fraction of water use air less than 5%) under the conditions of 40 DEG C
Source ozone machine is continually fed into ozone 5h with the flow of 8g/h, obtains ozonisation waste oil；
2) preparation of heat treatment ozonisation waste oil:
Ozonisation waste oil is heated into 8h under the conditions of 120 DEG C, ozonisation waste oil must be heat-treated.
Embodiment 17
A kind of method of modifying of grease, includes the following steps:
1) preparation of waste oil is ozonized:
Taking 80mL waste oil, (acid value 46.45mgKOH/g, the mass fraction of water use air less than 5%) under the conditions of 15 DEG C
Source ozone machine is continually fed into ozone 5h with the flow of 8g/h, obtains ozonisation waste oil；
2) preparation of heat treatment ozonisation waste oil:
Ozonisation waste oil is heated into 6h under the conditions of 100 DEG C, ozonisation waste oil must be heat-treated.
Embodiment 18
A kind of method of modifying of grease, includes the following steps:
1) preparation of waste oil is ozonized:
Taking 80mL waste oil, (acid value 46.45mgKOH/g, the mass fraction of water use air less than 5%) under the conditions of 15 DEG C
Source ozone machine is continually fed into ozone 5h with the flow of 8g/h, obtains ozonisation waste oil；
2) preparation of heat treatment ozonisation waste oil:
Ozonisation waste oil is heated into 8h under the conditions of 100 DEG C, ozonisation waste oil must be heat-treated.
Embodiment 19
A kind of method of modifying of grease, includes the following steps:
1) preparation of waste oil is ozonized:
Taking 80mL waste oil, (acid value 46.45mgKOH/g, the mass fraction of water use air less than 5%) under the conditions of 15 DEG C
Source ozone machine is continually fed into ozone 5h with the flow of 8g/h, obtains ozonisation waste oil；
2) preparation of heat treatment ozonisation waste oil:
Ozonisation waste oil is heated into 10h under the conditions of 100 DEG C, ozonisation waste oil must be heat-treated.
Embodiment 20
A kind of method of modifying of grease, includes the following steps:
1) preparation of waste oil is ozonized:
Taking 80mL waste oil, (acid value 46.45mgKOH/g, the mass fraction of water use air less than 5%) under the conditions of 15 DEG C
Source ozone machine is continually fed into ozone 2h with the flow of 6g/h, obtains ozonisation waste oil；
2) preparation of heat treatment ozonisation waste oil:
Ozonisation waste oil is heated into 25h under the conditions of 60 DEG C, ozonisation waste oil must be heat-treated.
Embodiment 21
A kind of method of modifying of grease, includes the following steps:
1) preparation of waste oil is ozonized:
Taking 80mL waste oil, (acid value 46.45mgKOH/g, the mass fraction of water use air less than 5%) under the conditions of 15 DEG C
Source ozone machine is continually fed into ozone 2h with the flow of 6g/h, obtains ozonisation waste oil；
2) preparation of heat treatment ozonisation waste oil:
Ozonisation waste oil is heated into 30h under the conditions of 120 DEG C, ozonisation waste oil must be heat-treated.
Embodiment 22
A kind of method of modifying of grease, includes the following steps:
1) preparation of waste oil is ozonized:
Taking 80mL waste oil, (acid value 46.45mgKOH/g, the mass fraction of water use air less than 5%) under the conditions of 15 DEG C
Source ozone machine is continually fed into ozone 2h with the flow of 6g/h, obtains ozonisation waste oil；
2) preparation of heat treatment ozonisation waste oil:
Ozonisation waste oil is heated into 30h under the conditions of 60 DEG C, ozonisation waste oil must be heat-treated.
Embodiment 23~44
A kind of coat fertilizer, preparation method are as follows:
Using the principle of industrial granulating disc, diameter is added in the open coating machine of the adjustable revolving speed of designed, designed
For the urea granules of 2~4.75mm, addition accounts for heat treatment ozonisation waste oil (embodiment 1,3,7~22) of urea quality 1.5%,
Properly increase revolving speed, to its urea surface after mixing, be added account for urea quality 5% 100 mesh of mistake ground phosphate rock, to it
After heat treatment ozonisation waste oil surface is evenly distributed (about 10min), it is useless that addition accounts for the heat treatment ozonisation of urea quality 1.8%
Oil, after add the ground phosphate rock for accounting for 100 mesh of mistake of urea quality 10%, rotating circular disc pelletizer is uniformly mixed it, and addition accounts for
The heat treatment ozonisation waste oil of urea quality 1.8%, mixes, the ground phosphate rock for accounting for 100 mesh of mistake of urea quality 10% is added, finally,
Addition accounts for the heat treatment ozonisation waste oil of urea quality 1.2%, and rotating circular disc pelletizer is uniformly mixed it, and addition accounts for urea quality
The ground phosphate rock of 10% 100 mesh of mistake keeps urea package tight, obtains heat treatment ozonisation waste oil base coat fertilizer, prepared packet
The nitrogen content of film fertilizer is about 32.55%, and the coat fertilizer that wherein prepared by embodiment 23 is as shown in Figure 2；
As shown in Figure 3: heat treatment ozonisation waste oil is in 3685cm-1Place generates characteristic absorption peak, and this feature absorption peak is hydroxyl
Base peak, and coating layer is in 3676cm-1Place generates hydroxyl characteristic absorption peak, by comparing with the hydroxyl peak of heat treatment ozonisation waste oil
It was found that it is mobile to low frequency range, this may be the PO due to-OH and rock phosphate in powder in heat treatment ozonisation waste oil4 3-Between generate hydrogen
Key active force generates hydrogen bond between substance, can enhance the tightness between coating layer, increases the hydrophobicity of the coat fertilizer of preparation
By force, slow release enhances.
It can be seen that the outer surface ground phosphate rock close adhesion of coat fertilizer by Fig. 4 a, there are minute quantity holes, it can be achieved that nutrient
Slow release.It can be seen that and bonded between the coating layer film layer closely by Fig. 4 b, between heat treatment ozonisation waste oil and ground phosphate rock
It is overlapped mutually, closely covers on urea, the quick release of urea can be hindered, to prevent the generation of plant burning root phenomenon.
Embodiment 45~62
A kind of coat fertilizer, preparation method are as follows:
Using the principle of industrial granulating disc, diameter is added in the open coating machine of the adjustable revolving speed of designed, designed
For the granular urea of 2~4.75mm, addition accounts for heat treatment ozonisation waste oil (embodiment 1,3,7~22) of urea quality 1.5%,
Revolving speed is properly increased, stays in urea surface after mixing, the composition silicate for accounting for 100 mesh of mistake of urea quality 5% is added；To
It ozonizes waste oil surface after mixing (about 10min) in heat treatment, and the heat treatment ozone for accounting for urea quality 1.4% is added
Change waste oil, add and account for 10% ground phosphate rock of urea quality, rotating circular disc pelletizer is uniformly mixed it, and addition accounts for urea quality
1.5% heat treatment ozonizes waste oil, mixes, and addition accounts for 9% ground phosphate rock of urea quality, accounts for urea quality 1.2% finally, being added
Heat treatment ozonize waste oil, rotating circular disc pelletizer make its be uniformly mixed, addition account for 10% ground phosphate rock of urea quality, make urea
Package is tight, obtains heat treatment ozonisation waste oil base coat fertilizer, the nitrogen content of prepared coat fertilizer is about 32.95%.
Embodiment 63~80
A kind of coat fertilizer, preparation method are as follows:
Using the principle of industrial granulating disc, diameter is added in the open coating machine of the adjustable revolving speed of designed, designed
For the granular urea of 2-4.75mm, addition accounts for heat treatment ozonisation waste oil (embodiment 1,3,7~22) of urea quality 1.5%,
Revolving speed is properly increased, stays in urea surface after mixing, addition accounts for urea quality 5% and crosses 80 mesh composition silicates；About
After 10min, addition accounts for the heat treatment ozonisation waste oil of urea quality 1.4%, adds and accounts for 10% ground phosphate rock of urea quality, rotation circle
Disk pelletizer is uniformly mixed it, and addition accounts for the heat treatment ozonisation waste oil of urea quality 1.7%, mixes, addition accounts for urea quality
11% ground phosphate rock accounts for the heat treatment ozonisation waste oil of urea quality 1.3% finally, being added, and rotating circular disc pelletizer keeps its mixing equal
Even, addition accounts for 10% ground phosphate rock of urea quality, keeps urea package tight, obtains heat treatment ozonisation waste oil base coat fertilizer, made
The nitrogen content of standby coat fertilizer is about 32.42%.
Embodiment 81~98
A kind of coat fertilizer, preparation method are as follows:
Using the principle of industrial granulating disc, diameter is added in the open coating machine of the adjustable revolving speed of designed, designed
For the granular urea of 2~4.75mm, addition accounts for heat treatment ozonisation waste oil (embodiment 1,3,7~22) of urea quality 1.5%,
Revolving speed is properly increased, stays in urea surface after mixing, addition accounts for urea quality 6% and crosses 120 mesh ground phosphate rock；About 10min
Afterwards, it is added and accounts for the heat treatment ozonisation waste oil of urea quality 1.8%, add and account for 10% ground phosphate rock of urea quality, rotating circular disc is made
Grain machine is uniformly mixed it, and addition accounts for the heat treatment ozonisation waste oil of urea quality 1.6%, mixes, addition accounts for urea quality 10%
Ground phosphate rock accounts for the heat treatment ozonisation waste oil of urea quality 1.2% finally, being added, and rotating circular disc pelletizer is uniformly mixed it, adds
Enter to account for 10% ground phosphate rock of urea quality, keep urea package tight, obtains heat treatment ozonisation waste oil base coat fertilizer, prepared packet
The nitrogen content of film fertilizer is about 32.37%.
Comparative example 1~4
A kind of coat fertilizer, preparation method are as follows:
Using the principle of industrial granulating disc, diameter is added in the open coating machine of the adjustable revolving speed of designed, designed
For the urea granules of 2~4.75mm, addition accounts for heat treatment ozonisation waste oil (embodiment 2,4~6) of urea quality 1.5%, fits
When improve revolving speed, to its urea surface after mixing, be added account for urea quality 5% 100 mesh of mistake ground phosphate rock, to its
After heat treatment ozonisation waste oil surface is evenly distributed (about 10min), it is useless that addition accounts for the heat treatment ozonisation of urea quality 1.8%
Oil, after add the ground phosphate rock for accounting for 100 mesh of mistake of urea quality 10%, rotating circular disc pelletizer is uniformly mixed it, and addition accounts for
The heat treatment ozonisation waste oil of urea quality 1.8%, mixes, the ground phosphate rock for accounting for 100 mesh of mistake of urea quality 10% is added, finally,
Addition accounts for the heat treatment ozonisation waste oil of urea quality 1.2%, and rotating circular disc pelletizer is uniformly mixed it, and addition accounts for urea quality
The ground phosphate rock of 10% 100 mesh of mistake keeps urea package tight, obtains heat treatment ozonisation waste oil base coat fertilizer, prepared packet
The nitrogen content of film fertilizer is about 32.55%.
The performance test of heat treatment ozonisation waste oil:
1, contact angle test:
The heat treatment of 0.09g Examples 1 to 6 is taken to ozonize waste oil in being prepared into liquid film on the filter paper of 7 × 10mm respectively,
It uniformly smears, is placed in baking oven 80 DEG C, after 30min, is tested, Examples 1 to 6 (respectively corresponds H-1, H-0, H-2~H-
6) result is shown in Fig. 5, and embodiment 1,3, the contact angle result of embodiment 7~22 are further recorded in table 1:
As shown in Figure 5: the contact angle of ozonisation waste oil (H-0) is 49.55 °, with the extension in heating reaction time, liquid
The contact angle of film constantly increases, and is sequentially increased to 51.73 °, 56.36 °, 57.39 °, 59.75 ° and 66.26 °, relatively ozonizes waste oil
It compares, contact angle is respectively increased 2.18 °, 6.81 °, 7.84 °, 10.2 ° and 16.71 °, this illustrates with the extension of reaction time,
The wetability of liquid film is gradually deteriorated, and hydrophobicity constantly enhances, this is because heat modification reduces polar group carboxyl, molecule
Amount increases, so that hydrophobicity enhances.
2, acid value is tested:
The acid value test result for implementing the heat treatment ozonisation waste oil that 1~6 is prepared is shown in Fig. 6, prepared by Examples 1 to 22
The acid value of obtained heat treatment ozonisation waste oil is also further recorded in table 2:
As shown in Figure 6: with the extension of heating time, there is continuous downward trend, acid in acid value after heat treatment
Value is reduced to 49.93mgKOH/g by 80.91mgKOH/g, when reacted between be 12h when, grease acid value appearance significantly reduce
Trend, this is primarily due in ozonisation waste oil containing a large amount of peroxide, and peroxide thermal stability is poor, and heating makes
It is decomposed, and obtains volatile acid, these small molecule acid and fatty acid occur polymerization reaction and free acid in system can be made to reduce, and is caused
Acid value decline, therefore, peroxide value and acid value reduce in heat treatment ozonisation waste oil.
3, stability test:
The ozonisation waste oil and heat treatment ozonisation waste oil that embodiment 1,3, embodiment 7~22 are prepared are at normal temperature
Contact angle is tested in placement process, the results are shown in Table 1:
Table 1 ozonizes the variation that different time contact angle (°) is placed in waste oil heat treatment front and back
As shown in Table 1: there is constantly decline with the increase of storage time in the only ozonisation waste oil modified through ozone, contact angle
Trend, especially there is faster decrease speed at first 5 days；Then thermally treated ozonisation waste oil again, contact angle relative to
There is the trend risen substantially in not thermally treated ozonisation waste oil, and the ascensional range having is very big, while after heat treatment
Waste oil is ozonized in placement process, contact angle varies less, this illustrates that heat treatment can be improved the hydrophobic of ozonisation waste oil
Property and stability.
4, the measure of merit of coat fertilizer:
Using heat treatment ozonisation waste oil as raw material, coat fertilizer is prepared, delays (control) according to HG/T4215-2011 and releases fertilizer test mark
Standard tests the preliminary solubility of different coat fertilizers.With coat fertilizer and water quality ratio 1:20, is placed in hydrostatic for 24 hours, measure its nitrogen
Plain dissolution rate is also initial stage nutrient release rate.
With the burst size of coat fertilizer in paradime thylaminobenzaldehyde colour developing spectrophotometry test hydrostatic, test wavelength is
420nm；The configuration of color developing agent: taking 2.00g paradime thylaminobenzaldehyde developer solution in 100mL dehydrated alcohol, and 10mL is added
Concentrated hydrochloric acid, 10min is stood after shaking up, takes 7 colorimetric cylinders that the urea of the 0.5g/L of 0,2,4,6,8,10,12ml is added respectively；
The color developing agent of 10mL is added into each colorimetric cylinder again, 7 colorimetric cylinders are settled to 25ml with distilled water, use purple after standing 20min
Outer visible spectrophotometer measures its absorbance value at 420nm, and made urea burst size standard curve is as shown in fig. 7, calculate
Obtain its corresponding calibration curve equation are as follows: Y=3.9857X+0.0004, R2=0.9999, wherein Y indicates absorbance, and X is indicated
Urea concentration, R2Indicate related coefficient, embodiment 23~40 that thus calibration curve equation is calculated and comparative example 1~4
The initial stage nutrient release rate of coat fertilizer is recorded in table 2:
Table 2 ozonizes the variation and coating effect of waste oil heat treatment front and back acid value and contact angle
As shown in Table 2: the acid value of heat treatment ozonisation waste oil is compared to raw material ozonisation waste oil (placing 5 days after preparation)
Acid value is decreased obviously, this illustrates that heating can promote the further modification of grease so that carboxyl therein is reduced, this with it is infrared
As a result consistent；Meanwhile the contact angle of the heat treatment ozonisation waste oil after further heat modification increases, this illustrates process
Further heat modification is conducive to the hydrophobicity of enhancing ozonisation waste oil, in addition, heat treatment ozonisation waste oil prepares coat fertilizer
Initial stage nutrient release rate is respectively less than 15%, meets the standard of the coated fertilizer of coat fertilizer, but the coat fertilizer initial stage of comparative example 2~4
Larger nutrient release rate may be that form it can not single because mutually bonding occurs in it during coating between coat fertilizer
Coat fertilizer particle, cause initial stage nutrient release rate increase.
Further, ozonisation waste oil and step 2) that 1,3,7~16 step 1) of embodiment is prepared are prepared
Heat treatment ozonisation waste oil according to the method that embodiment 23~44 prepares coat fertilizer prepare coat fertilizer, after test respectively it is freshly prepared
Coat fertilizer and the coat fertilizer after being placed 15 days under room temperature initial stage nutrient release rate, as a result see the table below 3:
Table 3 ozonizes waste oil and heat treatment ozonisation waste oil is the initial stage nutrient release rate (%) that raw material prepares coat fertilizer
Note: ozonisation waste oil is the product of raw material, places 5 days coat fertilizers prepared again for ozonisation waste oil；It is heat-treated smelly
The product that waste oil is raw material is aoxidized, reheating processing in 5 days is placed for ozonisation waste oil, prepares coat fertilizer at once later.
As shown in Table 3: merely through the modified coat fertilizer for ozonizing waste oil preparation of ozone after 15 days place, initial stage
There is different degrees of raising in nutrient release rate, and the coat fertilizer for passing through the ozonisation waste oil preparation being further heat-treated passes through
After 15 days place, there is no variations substantially for initial stage nutrient release rate, this illustrates the coating of heat treatment ozonisation waste oil preparation
Fertilizer has higher stability.
Claims (10)
1. a kind of method of modifying of grease, characterized by the following steps:
1) grease is modified using ozone, obtains ozonisation grease；
2) ozonisation grease is modified again under heating conditions, ozonisation grease must be heat-treated.
2. according to the method described in claim 1, it is characterized by: the mass fraction in the grease containing water is no more than 5%；
Preferably, the grease is the grease containing C=C functional group；Preferably, the grease is selected from waste grease.
3. method according to claim 1 or 2, it is characterised in that: the step 1) ozone is modified the grease
Temperature be 10~40 DEG C.
4. method according to claim 1 or 2, it is characterised in that: the volume ratio of step 1) ozone flow and the grease
For 0.15~1g/mL, the reaction time is 2~14h.
5. method according to claim 1 or 2, it is characterised in that: the heating temperature of step 2) is 60~120 DEG C, heating
Time is 6~30h.
6. the heat treatment ozonisation grease that method described in Claims 1 to 5 any one is prepared is as coated fertilizer
Using.
7. application according to claim 6, it is characterised in that: the heat treatment ozonisation grease is used for as coated fertilizer
Prepare coat fertilizer.
8. a kind of coat fertilizer, it is characterised in that: including fertilizer and positioned at the coated fertilizer of fertilizer outer layer, the coated fertilizer
Grease is ozonized comprising the heat treatment that method described in any one according to claim 1~5 is prepared.
9. coat fertilizer according to claim 8, it is characterised in that: the outer layer of the coat fertilizer includes multiple smelly by being heat-treated
Aoxidize the layer of grease composition and the reinforcing substance positioned at interlayer；The stiffener is of fine quality be selected as sulphur powder, biogas residue powder, phosphate,
At least one of silicate, charcoal, straw powder, bamboo charcoal, mineral powder, zeolite powder, bentonite, composition silicate.
10. coat fertilizer according to claim 9, it is characterised in that: the heat treatment ozonizes grease: fertilizer: stiffener
The mass ratio of matter is 0.4~1.2:10:3.3~4.1；Preferably, the fertilizer is the form of particle.
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| CN110786994A (en) * | 2019-10-24 | 2020-02-14 | 万明 | Double-component active oxygen bacteriostatic sanitary towel and preparation method thereof |
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