CN102942996A

CN102942996A - Method for preparing ink solvent by utilizing waste animal and plant grease

Info

Publication number: CN102942996A
Application number: CN2012104513341A
Authority: CN
Inventors: 李为民; 陆朝阳; 高琦; 许汉祥
Original assignee: JIANGSU GAOKE PETROCHEMICAL Co Ltd
Current assignee: Zhongsheng New Materials Technology Yixing Co ltd
Priority date: 2012-11-12
Filing date: 2012-11-12
Publication date: 2013-02-27
Anticipated expiration: 2032-11-12
Also published as: CN102942996B

Abstract

The invention discloses a method for preparing ink solvent by utilizing waste animal and plant grease, and the method is characterized in that waste animal and plant grease is used as raw materials, the waste animal and plant grease is firstly heated so as to dehydrate and remove the impurities, then the waste animal and plant grease has esterification reaction with alkyl alcohol to remove the acid under a high-temperature pressurizing condition and under the catalytic effect of the acidity catalyst, then decoloration is carried out, and decompression, distillation, deodorization and dehydration are carried out to obtain the pure esterified grease which can be used as the ink solvent. The pure esterified grease can substitute the pure plant grease to be used as the ink solvent, so that the production cost of ink can be reduced, and the reutilization of the resource can be realized. Meanwhile, fatty acid in the waste animal and plant grease is converted to aliphatic ester through the esterification reaction, so that the drying performance of the ink solvent can be greatly improved.

Description

A kind of method of utilizing waste animal and vegetable oil to prepare printing ink solvent

Technical field

The invention belongs to technical field of ink, relate to a kind of method of utilizing waste animal and vegetable oil to prepare printing ink solvent, particularly, the present invention adopts that waste animal and vegetable oil is assorted through dehydration, depickling, obtain pure esterification grease after decolouring, take off the refinement treatment such as flavor dehydration, is a kind of novel environment-friendly type printing ink solvent.

Background technology

Under the impact of nowadays sustainable economic development, resource problem and environmental issue obtain unprecedented attention, and green printing is just with its formidably influence power adjustment and guiding the development of global printing industry.Environment-friendly ink begins to use in the packages printings such as food, medicine in recent years, but in terms of overall, its range of application is still very limited.Want printing ink to meet environmental requirement, at first should change composition, namely adopt ep-type material preparation novel ink.At present, environment-friendly ink mainly contains water color ink, UV printing ink, soya-bean ink etc.

Water color ink is by specific aqueous high molecular resin, pigment, water, and adds auxiliary agent through the physical and chemical process combination and the printing ink of preparation, the abbreviation ink.The maximum difference of water color ink and solvent type ink, the solvent that is its use is water rather than organic solvent, after printing ink is transferred to stock, moisture evaporation is in environment or in the infiltration stock, printing ink is dry with the volatilization of moisture, the aqueous high molecular resin is the topmost integral part of water color ink, it mainly plays low-melting ink vehicle in ink, it makes the pigment can Uniform Dispersion, make printing ink have certain flowability, and adhesive power with printable fabric is provided, make printing ink can after printing, form uniform China ink layer.Its maximum advantage is not contain volatile organic solvent, and its use has reduced the amount of organic volatile, can not damage the health of ink manufacturers and press operator, has improved the quality of environment.But can occur usually in use that form and aspect are inaccurate, viscosity is unstable, rate of drying is unstable, be difficult to alignment, the problem such as bubbles of ink.

UV printing ink (being the UV curing curing inks) refers under the ultraviolet light irradiation of certain wavelength, the photon that Photoepolymerizationinitiater initiater in the printing ink absorbs certain wavelength can transfer the free radical of free state molecule to, transmission by intermolecular energy, make polymerizability prepolymer and photo-sensitive monomer become excited state, produce charge transfer complexing body, continuous crosslinking polymerization between the complexing body changes liquid printing ink moment into solid-state, thereby forms the printing ink of dry solidification.Its advantage is that rate of drying is fast, to save the energy, ink particle little etc.; Shortcoming is that wherein some compositions touch skin, can produce certain hormesis, even can cause allergicly, and UV light has certain injury to human body, also has ink residue to be difficult to the problems such as processing.

Soya-bean ink is plant oil based China ink, and it uses Vegetable oil lipoprotein as binder, and the binder of researching and developing at present and using mainly contains soybean oil, rapeseed oil, Oleum Gossypii semen, sunflower wet goods; Wherein the most frequently used is exactly soya-bean ink, by mixing such as soybean oil and resin, pigment auxiliary agents and make.Its main advantage has, and has reduced the material of volatile in the printing ink, and rub resistance and heat-resisting character are relatively good, and deinking is easy, and color and luster is good, and inking is good, and anti-radium-shine property is good, renewable etc.The people such as Henrik have proposed a kind of cleaning solvent of environment-friendly type for the printing ink (US 5104567) of Printing Industry.Wherein comprise 90 ~ 99% vegetables oil, especially soybean oil also has 1 ~ 10% tensio-active agent.This solvent can remove removal ink from printing press effectively, has substituted the solvent of petroleum chemicals, has improved the quality of Working environment.Will exceed more than 20% but compare price with traditional printing ink, drying property is also poor, and range of application is narrow.

Summary of the invention

In view of the higher problem of the cost of soya-bean ink, one of purpose of the present invention is to provide a kind of method of utilizing waste animal and vegetable oil to prepare printing ink solvent.The method is assorted through dewatering with waste animal and vegetable oil, esterification deacidification, obtain pure esterification grease after decolouring, take off process refining such as flavor dehydration etc., substitute pure Vegetable oil lipoprotein as printing ink solvent, to reduce production costs, and the lipid acid in the waste animal and vegetable oil is converted into fatty acid ester, improve the drying property of printing ink solvent, widened its range of application.

In order to achieve the above object, the present invention has adopted following technical scheme:

A kind of method of utilizing waste animal and vegetable oil to prepare printing ink solvent, described method comprises the steps:

(1) the waste animal and vegetable oil dehydration is assorted;

(2) will dewater product after assorted under the effect of an acidic catalyst, and with alkyl alcohol generation esterification, the acid number of waste animal and vegetable oil will be reduced to below the 1mgKOH/g waste animal and vegetable oil;

(3) with the decolouring of the product in the step (2), take off the flavor dehydration, obtain pure esterification grease.

Waste animal and vegetable oil of the present invention is preferred but be not limited to hogwash fat and/or sewer oil, anyly can't all can be used as raw material of the present invention by direct applied animal or plant grease.Wherein, hogwash fat is the residue leftovers of eating and drinking establishment, and the pulp water of the process oil traps such as dishwashing detergent water separates, fishes for oil reservoir, again by thermal dehydration, the grease that forms of refining treatment simply.And all kinds of poor quality oils in the life of sewer oil general reference, comprise surpass certain number of times with the greasy floating matter in the water drain or with the oil of the leftovers of hotel, restaurant, leftovers (common name swill) output through the oil (narrow sense sewer oil) of simply processing, extracting, pork inferior, haslet, pigskin processing and after refining or the oily access times that are used for fried food product after, be reused again or toward wherein adding the oil of reusing behind some fresh oils.

Preferably, described dehydration is mixed and is carried out under 60 ~ 80 ℃ of temperature, and for example 62 ℃, 64 ℃, 66 ℃, 68 ℃, 70 ℃, 72 ℃, 74 ℃, 76 ℃, 79 ℃, preferred 62 ~ 78 ℃, further preferred 65 ~ 75 ℃.

Preferably, the assorted time of described dehydration is 12 ~ 24 hours, for example 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, preferred 15 ~ 22 hours, further preferred 15 ~ 20 hours.

Waste animal and vegetable oil is 60 ~ 80 ℃ of lower insulations after 12 ~ 24 hours, and settlement separate moisture and the impurity that goes out in the waste animal and vegetable oil obtains the assorted product that dewaters.

The product that dehydration is assorted is under the effect of an acidic catalyst, with alkyl alcohol generation esterification, the acid number of waste animal and vegetable oil is reduced to below the 1mgKOH/g waste animal and vegetable oil, make the most lipid acid in the waste animal and vegetable oil be converted into fatty acid ester, improve the drying property of this printing ink solvent, widened its use range.Waste animal and vegetable oil in " the 1mgKOH/g waste animal and vegetable oil is following " is not the concept of waste animal and vegetable oil in the raw material, in esterification reaction process, esterification products is carried out the acid number test, until acid number meets the requirements, therefore, waste animal and vegetable oil is a dynamic concept herein, in fact it refer to esterification reaction product carried out the acid number tested object in test time, therefore, the those skilled in the art can very clearly determine the concept of waste animal and vegetable oil herein according to foregoing description, and can clearly understand the calculating of acid number.

Preferably, described an acidic catalyst is that liquid acid catalyst is or/and solid acid catalyst.

Preferably, described liquid acid catalyst is that sulfuric acid is or/and phosphoric acid.Described liquid acid catalyst for example is the mixture of sulfuric acid and phosphoric acid.

Preferably, described solid acid catalyst is sodium pyrosulfate, ferric sulfate, the mixture of any one in sal epsom or the calcium sulfate or at least two kinds, described mixture is the mixture of sodium pyrosulfate and ferric sulfate for example, the mixture of ferric sulfate and sal epsom, the mixture of sal epsom and calcium sulfate, sodium pyrosulfate, the mixture of ferric sulfate and sal epsom, ferric sulfate, the mixture of calcium sulfate and sal epsom, preferably sulfuric acid iron, the mixture of any one in calcium sulfate or the sal epsom or at least two kinds, further preferably sulfuric acid iron, calcium sulfate and sal epsom three's mixture.

Preferably, described an acidic catalyst is ferric sulfate, calcium sulfate and sal epsom three's mixture, the mass ratio of described ferric sulfate, sal epsom and calcium sulfate is (50 ~ 30): (20 ~ 30): (20 ~ 40), for example 35:25:25,40:28:30,45:28:38,30:30:40,45:20:30, the mass ratio of preferred described ferric sulfate, sal epsom and calcium sulfate is (50 ~ 30): (20 ~ 30): (30 ~ 40).Adopt the mixture of ferric sulfate, calcium sulfate and sal epsom as an acidic catalyst, catalytic esterification, this an acidic catalyst is insoluble in the organic reaction system, is easy to separate after reaction finishes, and has simplified separation and the aftertreatment technology of esterification products.The mixture of ferric sulfate, calcium sulfate and sal epsom is solid acid catalyst as an acidic catalyst, obtains esterification reaction product with can filtering after the waste animal and vegetable oil contact reacts.Simultaneously, this esterification reaction product does not need to wash the process of removing catalyzer again, produces sewage few.If use conventional sulfuric acid catalyst, large to equipment corrosion, also to wash to remove a small amount of sulfuric acid that is present in the esterification products to esterification products, produce a large amount of industrial sewages.

The quality of described an acidic catalyst is 1 ~ 5% of step (1) quality of sloughing the assorted product of water, for example 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, and preferred 1 ~ 4%, further preferred 1 ~ 3%.

Described alkyl alcohol is the monobasic low-carbon alcohol, the monohydroxy-alcohol of preferred 1 ~ 6 carbon atom, the further monohydroxy-alcohol of preferred 1 ~ 4 atom, the further mixture of any one in particular methanol, ethanol, butanols or the Virahol or at least two kinds.Described mixture is the mixture of methyl alcohol and ethanol for example, the mixture of ethanol and butanols, the mixture of butanols and Virahol, the mixture of methyl alcohol, ethanol and butanols, the mixture of ethanol, butanols and Virahol.

The quality of described alkyl alcohol is 10 ~ 30% of step (1) quality of sloughing the assorted product of water, for example 12%, 14%, 16,18%, 20%, 22%, 24%, 26%, 28%, 29%, and preferred 12 ~ 28%, further preferred 15 ~ 25%.

The temperature of described esterification is high temperature with respect to the boiling point of alkyl alcohol, the temperature of esterification is 100 ~ 150 ℃, for example 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, preferred 105 ~ 145 ℃, further preferred 110 ~ 140 ℃.

The time of described esterification is 0.2 ~ 2 hour, for example 0.3 hour, 0.5 hour, 0.7 hour, 0.9 hour, 1.1 hours, 1.3 hours, 1.5 hours, 1.7 hours, 1.9 hours, and preferred 0.4 ~ 1.8 hour, further preferred 0.6 ~ 1.4 hour.

Described esterification is low pressure reaction, and pressure is 0.2 ~ 1MPa, for example 0.3MPa, 0.4MPa, 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa, preferred 0.3 ~ 0.9MPa, further preferred 0.4 ~ 0.6MPa.

For the speed of enhance esterification, carry out stirring operation in the described esterification reaction process.

In esterification finishes, shift out reaction solution, air distillation goes out excessive alkyl alcohol and moisture, separates and removes an acidic catalyst, and the supernatant liquid that obtains is the product of step (2) esterification.

The described decoloring reaction of step (3) is realized by add discoloring agent in the product of step (2), described discoloring agent is selected from the mixture of any one or at least two kinds in gac, hydrogen peroxide or the atlapulgite, for example, the product of step (2) can be first with behind the activated carbon decolorizing, use again activated decoloration, perhaps first with after the hydrogen peroxide decolouring, again with activated carbon decolorizing etc., the preferred hydrogen peroxide of described discoloring agent is or/and gac, further preferred hydrogen peroxide.Can improve the color and luster of waste animal and vegetable oil by decolouring, improve simultaneously the smell of waste animal and vegetable oil.The concentration of described hydrogen peroxide is 30 ~ 50%, for example 32%, 34%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, and preferred 31 ~ 45%, further preferred 35 ~ 45%.Hydrogen peroxide is the aqueous solution of hydrogen peroxide, the concentration of described hydrogen peroxide namely: the massfraction of hydrogen peroxide in the aqueous solution.

The quality of described hydrogen peroxide be step (2) product quality 3 ~ 20%, for example 5%, 7%, 9,11%, 13%, 15%17%, 19%, preferred 4 ~ 18%, further preferred 6 ~ 15%.

The temperature of described decoloring reaction is 60 ~ 80 ℃, for example 61 ℃, 63 ℃, 67 ℃, 69 ℃, 71 ℃, 73 ℃, 76 ℃, 78 ℃, and preferred 62 ~ 78 ℃, further preferred 65 ~ 75 ℃.

Preferably, the decolouring of employing hydrogen peroxide, the time of described hydrogen peroxide decoloring reaction is 0.5 ~ 1 hour, for example 0.55 hour, 0.6 hour, 0.65 hour, 0.7 hour, 0.75 hour, 0.8 hour, 0.85 hour, 0.9 hour, 0.95 hour, preferred 0.55 ~ 0.95 hour, further preferred 0.6 ~ 0.9 hour.

Preferably, adopt activated carbon decolorizing, the quality of described gac be step (2) product quality 0.2 ~ 2%, for example 0.3%, 0.5%, 0.7%, 0.9%, 1.1%, 1.3%, 1.5%, 1.7%, preferred 0.3 ~ 1.2%, further preferred 0.5 ~ 1.0%.Preferably, adopt activated carbon decolorizing, the temperature of described activated carbon decolorizing reaction is 80 ~ 100 ℃, for example 82 ℃, 84 ℃, 86 ℃, 88 ℃, and 90 ℃, 92 ℃, 94 ℃, 96 ℃, 98 ℃, preferred 85 ~ 95 ℃.

Preferably, adopt activated carbon decolorizing, the time of described activated carbon decolorizing reaction is 0.2 ~ 1 hour, for example 0.3 hour, 0.5 hour, 0.7 hour, and preferred 0.4 ~ 0.6 hour.

Preferably, adopt activated decoloration, the quality of described atlapulgite be step (2) product quality 0.5 ~ 5%, such as 0.6%, 0.9%, 1.2%, 1.5%, 1.8%, 2.1%, 2.4%, 2.7%, 3.0%, 3.3%, 3.6%, 3.9%, 4.2%, 4.5%, 4.8% etc., preferred 1 ~ 4%, further preferred 2 ~ 3%.

Preferably, adopt activated decoloration, the temperature of described gac carclazyte decoloring reaction is 90 ~ 110 ℃, for example 92 ℃, 94 ℃, 96 ℃, 98 ℃, 100 ℃, 102 ℃, 104 ℃, 106 ℃, 108 ℃, and preferred 95 ~ 105 ℃.

Preferably, adopt activated decoloration, the time of described activated decoloration reaction is 0.2 ~ 1 hour, for example 0.3 hour, 0.5 hour, 0.7,0.9 hour, and preferred 0.4 ~ 0.6 hour.

After the decolouring of the product in the step (2), separate and remove water (discoloring agent and water etc.), the product after obtaining decolouring.Product after the decolouring is taken off the flavor dehydration.The described flavor that takes off dewaters by the underpressure distillation realization, can further remove moisture, and can further improve the smell of waste animal and vegetable oil.The pressure of described underpressure distillation is negative pressure, pressure is-0.1 ~ 0MPa, for example-0.02MPa ,-0.03MPa ,-0.04MPa ,-0.05MPa ,-0.06MPa ,-0.07MPa ,-0.08MPa ,-0.09MPa ,-0.099MPa, preferably-0.098 ~-0.085MPa, further preferred-0.095 ~-0.08MPa.The temperature of described underpressure distillation is 60 ~ 100 ℃, for example 65 ℃, 70 ℃, 75 ℃, 80 ℃, 86 ℃, 91 ℃, 96 ℃, 99 ℃, and preferred 68 ~ 94 ℃, further preferred 72 ~ 90 ℃.

Preferably, described decolouring, take off flavor dehydration and carry out simultaneously, preferably adopt first the hydrogen peroxide decolouring, and then in hydrogen peroxide decolouring product, add gac or atlapulgite, carry out underpressure distillation, realize decolouring, carry out when taking off flavor and dehydration.

The product that takes off after flavor dewaters is pure esterification grease, can be used as printing ink solvent.

The typical but non-limiting method of utilizing waste animal and vegetable oil to prepare printing ink solvent of the present invention comprises the steps:

(1) waste animal and vegetable oil is incubated 12 ~ 24 hours under 60 ~ 80 ℃, finishes dehydration assorted;

(2) will dewater assorted product under the effect of an acidic catalyst, be under the condition of 0.2 ~ 1MPa esterification 0.2 ~ 2 hour to occur at 100 ~ 150 ℃, pressure with alkyl alcohol, the acid number of waste animal and vegetable oil is reduced to below the 1mgKOH/g waste animal and vegetable oil; Wherein, described an acidic catalyst is the mixture of ferric sulfate, calcium sulfate and sal epsom, the mass ratio of ferric sulfate, sal epsom and calcium sulfate is 30 ~ 50:20 ~ 30:20 ~ 40, the quality of an acidic catalyst be the assorted product of step (1) dehydration quality 1 ~ 5%, alkyl alcohol is the mixture of any one or at least two kinds in methyl alcohol, ethanol, butanols or the Virahol, the quality of alkyl alcohol be the assorted product of step (1) dehydration quality 10 ~ 30%;

(3) in the product of step (2), add 3 ~ 20% the hydrogen peroxide of quality that quality is the product of step (2), 60 ~ 80 ℃ of lower decolourings 0.5 ~ 1 hour, the concentration of described hydrogen peroxide is 30 ~ 50%, after the decolouring, take off the flavor dehydration by underpressure distillation, the pressure of described underpressure distillation is-0.1 ~ 0MPa, and temperature is 60 ~ 100 ℃, after taking off the flavor dehydration, obtain pure esterification grease.This esterification grease is carried out the physicochemical property test, and it can be used as printing ink solvent.

Two of purpose of the present invention is to provide a kind of purposes that adopts the esterification grease that aforesaid method prepares, and this esterification grease is as printing ink solvent.The esterification grease that adopts method as mentioned above to prepare is carried out the physicochemical property test, such as performances such as acid number, saponification value, iodine numbers, find that the physicochemical property of this esterification grease is extremely outstanding, be suitable for very much preparing printing ink.This esterification grease is a kind of novel environment-friendly type printing ink solvent.

Three of purpose of the present invention is to provide a kind of printing ink, and described printing ink comprises the esterification grease that adopts aforesaid method to prepare.In this printing ink, the esterification grease uses as printing ink solvent.The preparation method of described printing ink is the prior art of this area, and the those skilled in the art can with reference to the preparation method of disclosed printing ink in the prior art, prepare this printing ink.

Compared with prior art, the present invention has following beneficial effect:

(1) the present invention adopts waste animal and vegetable oil is assorted through dewatering, esterification deacidification, obtains pure esterification grease after decolouring, take off the process refining such as flavor, substitute pure Vegetable oil lipoprotein as printing ink solvent, reduce the production cost of printing ink, and realized the recycling of resource;

(2) printing ink that the esterification grease that adopts method of the present invention to obtain prepares does not contain organic solvent, and environmentally safe is environment-friendly type printing ink;

(3) printing ink that the esterification grease that adopts method of the present invention to obtain prepares, its wear resistance and Good Heat-resistance, and deinking is easy;

(4) the method for the invention is converted into fatty acid ester by esterification with the lipid acid in the waste animal and vegetable oil, has greatly improved the drying property of printing ink solvent.

Description of drawings

Further specify technical scheme of the present invention below in conjunction with accompanying drawing and by embodiment.

Fig. 1: utilize waste animal and vegetable oil to prepare the process flow sheet of solvent ink among the embodiment 1-4.

Embodiment

For the present invention is described better, be convenient to understand technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows:

Be illustrated in figure 1 as the process flow sheet that utilizes waste animal and vegetable oil to prepare solvent ink, described catalyzer is an acidic catalyst of the present invention.

Embodiment 1

Sewer oil 200g(acid number 13.6KOH/g sewer oil after dehydration is assorted, the golden yellow color look) adds in the 500ml enclosed high pressure reactor, to wherein adding 15% methyl alcohol that quality is sewer oil, (ferric sulfate: sal epsom: calcium sulfate=50:20:30) quality is 3% of sewer oil to an acidic catalyst, be heated to 125 ℃, pressure 0.4MPa, rapid stirring half hour, then shift out reaction solution, air distillation goes out unnecessary methyl alcohol and moisture, remove catalyzer by separating, get supernatant liquid, acid number is the 0.49gKOH/g sewer oil;

Be 35% hydrogen peroxide 12% to wherein dripping concentration under 60 ℃, stirring reaction 0.5 hour, stopped reaction separates and removes water (hydrogen peroxide, water etc.);

Above-mentioned reacted product, 80 ℃ ,-0.09MPa under and underpressure distillation 1h, remove moisture and smell, obtain drying, pure esterification grease.

Its physico-chemical property is as follows after measured, can be used as printing ink solvent.

The physico-chemical property of table 1 esterification grease

Project	Index
		Acid number/(mg/g)	0.49
Saponification value/(mg/g)	180
		Iodine number/(g/100g)	130
Viscosity/mPas	45
		Smell	Free from extraneous odour
Color and luster	Y60，R5
		Peroxide value/(mmol/100g)	1.8
Insoluble impurities	0.01%
		Moisture	0.02%
Transparency	Clear

Embodiment 2

Hogwash fat 200g(acid number 9.6KOH/g oil after dehydration is assorted, color and luster is yellow) add in the 500ml enclosed high pressure reactor, to wherein adding 20% ethanol that quality is hogwash fat, an acidic catalyst (ferric sulfate: sal epsom: calcium sulfate=40:30:30) quality is the 2%(w of hogwash fat), be heated to 145 ℃, pressure 0.6MPa stirred 1 hour, then shifted out reaction solution, air distillation goes out unnecessary alcohol and moisture, remove catalyzer by separating, get supernatant liquid, acid number is the 0.32gKOH/g hogwash fat;

Be 35% hydrogen peroxide 8% to wherein dripping concentration under 70 ℃, stirring reaction 0.5 hour, stopped reaction separates and removes water (hydrogen peroxide, water etc.);

Above-mentioned reacted product, 70 ℃ ,-0.095MPa under and reduced vacuum distillation 1h, remove moisture and smell, obtain drying, pure esterification grease.

Table 2 esterification grease physico-chemical property

Embodiment 3

Hogwash fat 200g(acid number 22.6KOH/g oil after dehydration is assorted, color and luster is yellow) add in the 500ml enclosed high pressure reactor, to wherein adding 20% butanols that quality is hogwash fat, (ferric sulfate: sal epsom: calcium sulfate=50:30:20) quality is 2% of hogwash fat to an acidic catalyst, be heated to 150 ℃, pressure 0.6MPa stirred 1 hour, then shifted out reaction solution, air distillation goes out unnecessary butanols and moisture, remove catalyzer by separating, get supernatant liquid, acid number is the 0.45gKOH/g hogwash fat;

Be 35% hydrogen peroxide 10% to wherein dripping concentration under 70 ℃, stirring reaction 0.5 hour, stopped reaction separates and removes water (hydrogen peroxide, water etc.);

Above-mentioned reacted product, 80 ℃ ,-0.095MPa under and reduced vacuum distillation 1h, remove moisture and smell, obtain drying, pure esterification grease.

Table 3 esterification grease physico-chemical property

Project	Index
		Acid number/(mg/g)	0.32
Saponification value/(mg/g)	173
		Iodine number/(g/100g)	128
Viscosity/mPas	51
		Smell	Free from extraneous odour
Color and luster	Y70，R3
		Refractive index	1.4624
Insoluble impurities	0.01%
		Moisture	0.01%
Transparency	Clear

Embodiment 4

Sewer oil 200g(acid number 25.4KOH/g oil after dehydration is assorted, the golden yellow color look) add in the 500ml enclosed high pressure reactor, to wherein adding 20% Virahol that quality is sewer oil, (ferric sulfate: sal epsom: calcium sulfate=30:30:40) quality is 4% of sewer oil to an acidic catalyst, be heated to 130 ℃, pressure 0.6MPa stirred 1 hour, then shifted out reaction solution, air distillation goes out unnecessary butanols and moisture, remove catalyzer by separating, get supernatant liquid, acid number is the 0.32gKOH/g sewer oil;

Be 35% hydrogen peroxide 15% to wherein dripping concentration under 70 ℃, stirring reaction 0.5 hour, stopped reaction separates and removes water (hydrogen peroxide, water etc.);

Table 4 esterification grease physico-chemical property

Project	Index
		Acid number/(mg/g)	0.32
Saponification value/(mg/g)	179
		Iodine number/(g/100g)	131
Viscosity/mPas	47
		Smell	Free from extraneous odour
Color and luster	Y70，R3
		Insoluble impurities	0.01%
Moisture	0.01%
		Transparency	Clear

Embodiment 5

The esterification oil and fat preparation printing ink that uses embodiment 1 to prepare, specifically fill a prescription as follows:

Table 5 ink formulations

Project	Mass percent %
		The esterification grease	25

Tung oil	10
		Resol	35
Pigment	13
		Stopping composition	10
Other auxiliary agents	7
		Add up to	100

Survey its physico-chemical property as follows:

Table 6 printing ink physico-chemical property

Embodiment 6

With the sewer oil 200g(acid number 25.4KOH/g oil after 60 ℃ of dehydrations assorted 24 as a child, the golden yellow color look) adds in the 500ml enclosed high pressure reactor, to wherein adding 30% butanols that quality is sewer oil, (ferric sulfate: sal epsom: calcium sulfate=30:30:40) quality is 1% of sewer oil to an acidic catalyst, be heated to 100 ℃, pressure 1MPa, stirred 2 hours, then shift out reaction solution, air distillation goes out unnecessary butanols and moisture, remove catalyzer by separating, get supernatant liquid, acid number is the 0.35gKOH/g sewer oil;

Be 30% hydrogen peroxide 20% to wherein dripping concentration under 60 ℃, stirring reaction 1 hour, stopped reaction separates and removes water (hydrogen peroxide, water etc.);

Above-mentioned reacted product, 60 ℃ ,-0.098MPa under and reduced vacuum distillation 1h, remove moisture and smell, obtain drying, pure esterification grease.

Table 7 esterification grease physico-chemical property

Project	Index
		Acid number/(mg/g)	0.35
Saponification value/(mg/g)	175
		Iodine number/(g/100g)	130
Viscosity/mPas	46
		Smell	Free from extraneous odour
Color and luster	Y70，R3
		Insoluble impurities	0.01%
Moisture	0.01%
		Transparency	Clear

Embodiment 7

With the sewer oil 200g(acid number 25.4KOH/g oil after 80 ℃ of dehydrations assorted 12 as a child, the golden yellow color look) adds in the 500ml enclosed high pressure reactor, to wherein adding 20% butanols that quality is sewer oil, (ferric sulfate: sal epsom: calcium sulfate=30:30:40) quality is 5% of sewer oil to an acidic catalyst, be heated to 150 ℃, pressure 0.2MPa, stirred 0.2 hour, then shift out reaction solution, air distillation goes out unnecessary butanols and moisture, remove catalyzer by separating, get supernatant liquid, acid number is the 0.36gKOH/g sewer oil;

Be 35% hydrogen peroxide 3% to wherein dripping concentration under 80 ℃, stirring reaction 0.8 hour, stopped reaction separates and removes water (hydrogen peroxide, water etc.);

Under the above-mentioned reacted product, 100 ℃, 0MPa and underpressure distillation 1h, remove moisture and smell, obtain drying, pure esterification grease.

Table 8 esterification grease physico-chemical property

Project	Index
		Acid number/(mg/g)	0.36
Saponification value/(mg/g)	175
		Iodine number/(g/100g)	130
Viscosity/mPas	46
		Smell	Free from extraneous odour
Color and luster	Y70，R3
		Insoluble impurities	0.01%
Moisture	0.01%
		Transparency	Clear

Embodiment 8

Hogwash fat 200g(acid number 22.6KOH/g oil after dehydration is assorted, color and luster is yellow) add in the 500ml enclosed high pressure reactor, to wherein adding 20% butanols that quality is hogwash fat, (ferric sulfate: sal epsom: calcium sulfate=50:30:20) quality is 2% of hogwash fat to composite catalyst, be heated to 150 ℃, pressure 0.6MPa stirred 1 hour, then shifted out reaction solution, air distillation goes out unnecessary butanols and moisture, remove catalyzer by separating, get supernatant liquid, acid number is the 0.45gKOH/g hogwash fat;

Be 30% hydrogen peroxide 20% to wherein dripping concentration under 65 ℃, stirring reaction 1 hour, stopped reaction separates and removes water (hydrogen peroxide, water etc.);

Under 90 ℃ to wherein adding gac, quality of activated carbon is 1% of above-mentioned esterification products, 90 ℃ ,-0.095MPa under and reduced vacuum stir distillation 1h, decolour, remove moisture and smell, isolate gac after the end, obtain drying, pure esterification grease.

Table 9 esterification grease physico-chemical property

Embodiment 9

With the sewer oil 200g(acid number 25.4KOH/g oil after 60 ℃ of dehydrations assorted 24 as a child, the golden yellow color look) adds in the 500ml enclosed high pressure reactor, to wherein adding 30% butanols that quality is sewer oil, (ferric sulfate: sal epsom: calcium sulfate=30:20:40) quality is 1% of sewer oil to an acidic catalyst, be heated to 100 ℃, pressure 1MPa, stirred 2 hours, then shift out reaction solution, air distillation goes out unnecessary butanols and moisture, remove catalyzer by separating, get supernatant liquid, acid number is the 0.35gKOH/g sewer oil;

Under 80 ℃ to the gac that wherein adds esterification products 2%, stirring reaction 0.2 hour, stopped reaction separate to be removed gac;

Above-mentioned reacted product, 60 ℃ ,-0.095MPa under and reduced vacuum distillation 1h, remove moisture and smell, obtain drying, pure esterification grease.

Table 10 esterification grease physico-chemical property

Embodiment 10

With the sewer oil 200g(acid number 25.4KOH/g oil after 80 ℃ of dehydrations assorted 12 as a child, the golden yellow color look) adds in the 500ml enclosed high pressure reactor, to wherein adding 20% butanols that quality is sewer oil, (ferric sulfate: sal epsom: calcium sulfate=30:30:20) quality is 5% of sewer oil to an acidic catalyst, be heated to 150 ℃, pressure 0.2MPa, stirred 0.2 hour, then shift out reaction solution, air distillation goes out unnecessary butanols and moisture, remove catalyzer by separating, get supernatant liquid, acid number is the 0.36gKOH/g sewer oil;

Under 100 ℃ to the gac that wherein adds esterification products quality 0.2%, stirring reaction 1 hour, stopped reaction separate to be removed gac;

Above-mentioned reacted product, 100 ℃ ,-0.02MPa under and underpressure distillation 1h, remove moisture and smell, obtain drying, pure esterification grease.

Table 11 esterification grease physico-chemical property

Embodiment 11

Hogwash fat 200g(acid number 22.6KOH/g oil after dehydration is assorted, color and luster is yellow) add in the 500ml enclosed high pressure reactor, to wherein adding 20% butanols that quality is hogwash fat, (ferric sulfate: sal epsom: calcium sulfate=50:20:20) quality is 2% of hogwash fat to composite catalyst, be heated to 150 ℃, pressure 0.6MPa stirred 1 hour, then shifted out reaction solution, air distillation goes out unnecessary butanols and moisture, remove catalyzer by separating, get supernatant liquid, acid number is the 0.45gKOH/g hogwash fat;

Be benchmark to wherein adding the above-mentioned esterification products quality of atlapulgite 3%(under 90 ℃), 90 ℃ ,-0.095MPa under and reduced vacuum stir distillation 1h, moisture and smell decoloured, removed, isolate atlapulgite after the end, drying, pure esterification grease obtained.Its physico-chemical property is as follows after measured, can be used as printing ink solvent.

Table 12 esterification grease physico-chemical property

Embodiment 12

Under 110 ℃ to the atlapulgite that wherein adds esterification products 0.5%, stirring reaction 1 hour, stopped reaction separate to be removed atlapulgite;

Table 13 esterification grease physico-chemical property

Embodiment 13

Under 90 ℃ to the atlapulgite that wherein adds esterification products 5%, stirring reaction 0.2 hour, stopped reaction separate to be removed atlapulgite;

Above-mentioned reacted product, 90 ℃ ,-0.095MPa under and reduced vacuum distillation 1h, remove moisture and smell, obtain drying, pure esterification grease.

Table 14 esterification grease physico-chemical property

Embodiment 14

Under 100 ℃ to the atlapulgite that wherein adds esterification products 2%, stirring reaction 0.5 hour, stopped reaction separate to be removed atlapulgite;

Above-mentioned reacted product, 75 ℃ ,-0.098MPa under and reduced vacuum distillation 1h, remove moisture and smell, obtain drying, pure esterification grease.

Table 15 esterification grease physico-chemical property

Applicant's statement, the present invention illustrates method detailed of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned method detailed, does not mean that namely the present invention must rely on above-mentioned method detailed and could implement.The person of ordinary skill in the field should understand, any improvement in the present invention to the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.

Claims

1. a method of utilizing waste animal and vegetable oil to prepare printing ink solvent is characterized in that, described method comprises the steps:

(1) the waste animal and vegetable oil dehydration is assorted;

(2) will dewater assorted product under the effect of an acidic catalyst, and with alkyl alcohol generation esterification, the acid number of waste animal and vegetable oil will be reduced to below the 1mgKOH/g waste animal and vegetable oil;

2. the method for claim 1 is characterized in that, described waste animal and vegetable oil comprises hogwash fat and/or sewer oil;

Preferably, described dehydration is mixed and is carried out under 60 ~ 80 ℃ of temperature, and preferred 62 ~ 78 ℃, further preferred 65 ~ 75 ℃;

Preferably, the assorted time of described dehydration is 12 ~ 24 hours, preferred 15 ~ 22 hours, and further preferred 15 ~ 20 hours.

3. method as claimed in claim 1 or 2 is characterized in that, described an acidic catalyst is that liquid acid catalyst is or/and solid acid catalyst;

Preferably, described liquid acid catalyst is that sulfuric acid is or/and phosphoric acid; Preferably, described solid acid catalyst is the mixture of any one or at least two kinds in sodium pyrosulfate, ferric sulfate, sal epsom or the calcium sulfate, the mixture of any one in preferably sulfuric acid iron, calcium sulfate or the sal epsom or at least two kinds, further preferably sulfuric acid iron, calcium sulfate and sal epsom three's mixture;

Preferably, described an acidic catalyst is ferric sulfate, calcium sulfate and sal epsom three's mixture, the mass ratio of described ferric sulfate, sal epsom and calcium sulfate is (50 ~ 30): (20 ~ 30): (20 ~ 40), and the mass ratio of preferred described ferric sulfate, sal epsom and calcium sulfate is (50 ~ 30): (20 ~ 30): (30 ~ 40);

Preferably, the quality of described an acidic catalyst be step (1) slough the assorted product quality of water 1 ~ 5%, preferred 1 ~ 4%, further preferred 1 ~ 3%.

4. such as the described method of one of claim 1-3, it is characterized in that, described alkyl alcohol is the monobasic low-carbon alcohol, the monohydroxy-alcohol of preferred 1 ~ 6 carbon atom, the further monohydroxy-alcohol of preferred 1 ~ 4 atom, the further mixture of any one in particular methanol, ethanol, butanols or the Virahol or at least two kinds;

Preferably, the quality of described alkyl alcohol be step (1) slough the assorted product quality of water 10 ~ 30%, preferred 12 ~ 28%, further preferred 15 ~ 25%.

5. such as the described method of one of claim 1-4, it is characterized in that, the temperature of described esterification is 100 ~ 150 ℃, preferred 105 ~ 145 ℃, and further preferred 110 ~ 140 ℃;

The time of described esterification is 0.2 ~ 2 hour, preferred 0.4 ~ 1.8 hour, and further preferred 0.6 ~ 1.4 hour;

Preferably, the pressure of described esterification is 0.2 ~ 1MPa, preferred 0.3 ~ 0.9MPa, further preferred 0.4 ~ 0.6MPa.

6. such as the described method of one of claim 1-5, it is characterized in that, the described decolouring of step (3) realizes by add discoloring agent in the product of step (2), described discoloring agent is selected from the mixture of any one or at least two kinds in gac, hydrogen peroxide or the atlapulgite, preferred hydrogen peroxide is or/and gac, further preferred hydrogen peroxide.

7. method as claimed in claim 6 is characterized in that, the concentration of described hydrogen peroxide is 30 ~ 50%, preferred 31 ~ 45%, further preferred 35 ~ 45%;

Preferably, the quality of described hydrogen peroxide be step (2) product quality 3 ~ 20%, preferred 4 ~ 18%, further preferred 6 ~ 15%.

8. method as claimed in claim 5 is characterized in that, adopts the hydrogen peroxide decolouring, and the temperature of described hydrogen peroxide decoloring reaction is 60 ~ 80 ℃, preferred 62 ~ 78 ℃, and further preferred 65 ~ 75 ℃;

Preferably, adopt the hydrogen peroxide decolouring, the time of described hydrogen peroxide decolouring is 0.5 ~ 1 hour, preferred 0.55 ~ 0.95 hour, and further preferred 0.6 ~ 0.9 hour;

Preferably, adopt activated carbon decolorizing, the quality of described gac be step (2) product quality 0.2 ~ 2%, preferred 0.3 ~ 1.2%, further preferred 0.5 ~ 1.0%;

Preferably, adopt activated carbon decolorizing, the temperature of described activated carbon decolorizing reaction is 80 ~ 100 ℃, preferred 85 ~ 95 ℃;

Preferably, adopt activated carbon decolorizing, the time of described activated carbon decolorizing reaction is 0.2 ~ 1 hour, preferred 0.4 ~ 0.6 hour;

Preferably, adopt activated decoloration, the quality of described atlapulgite be step (2) product quality 0.5 ~ 5%, preferred 1 ~ 4%, further preferred 2 ~ 3%;

Preferably, adopt activated decoloration, the temperature of described gac carclazyte decoloring reaction is 90 ~ 110 ℃, preferred 95 ~ 105 ℃;

Preferably, adopt activated decoloration, the time of described activated decoloration reaction is 0.2 ~ 1 hour, preferred 0.4 ~ 0.6 hour;

Preferably, describedly take off flavor dehydration and realize by underpressure distillation, the pressure of described underpressure distillation be-0.1 ~ 0MPa, preferred-0.098 ~-0.085MPa, further preferably-0.095 ~-0.08MPa;

Preferably, the described flavor that takes off dewaters by the underpressure distillation realization, and the temperature of described underpressure distillation is 60 ~ 100 ℃, and preferred 68 ~ 94 ℃, further preferred 72 ~ 90 ℃;

9. the purposes of the esterification grease for preparing of the described method of one of an employing such as claim 1-8 is characterized in that, described esterification grease is as printing ink solvent.

10. a printing ink is characterized in that, described printing ink comprises the esterification grease that employing prepares such as the described method of one of claim 1-8.