CN110078591A - The method of refining crude glycerin - Google Patents
The method of refining crude glycerin Download PDFInfo
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- CN110078591A CN110078591A CN201910380771.0A CN201910380771A CN110078591A CN 110078591 A CN110078591 A CN 110078591A CN 201910380771 A CN201910380771 A CN 201910380771A CN 110078591 A CN110078591 A CN 110078591A
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- Prior art keywords
- glycerol
- catalyst
- acid
- ether
- crude glycerin
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
- C07C29/92—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound by a consecutive conversion and reconstruction
Abstract
The invention discloses a kind of methods of refining crude glycerin, are related to technical field of chemical synthesis.The method comprising the steps of: tert-butyl donor, crude glycerine are pressed the mass ratio of the material 1-10:1 by S1, carry out etherification reaction under solid acid catalyst effect, obtain glycerol tertbutyl ether through vacuum distillation；Glycerol tertbutyl ether is carried out cracking reaction under solid acid catalyst catalysis and obtains glycerol by S2, after the glycerol methanol dilution, is separated by filter membrane with catalyst；Emathlite is added into the efflux and obtains mixture by S3, and the Emathlite is the 2-3% of mixture quality, is sufficiently stirred, and neutralizes, filtering, filtrate is distilled, be concentrated after obtain high-purity glycerol.Wherein, the solid acid catalyst is acid resin catalyst or the immobilized acid catalyst of carrier.The present invention generates the method for glycerol using direct reaction to obtain the glycerol of purification, avoids neutralization in traditional separating technology, centrifugation, multistage distillation/rectifying, simple process and low cost.
Description
Technical field
The present invention relates to technical field of chemical synthesis more particularly to the synthetic methods of refining crude glycerin.
Background technique
Glycerol, i.e. glycerine, the general chemical property with ternary alcohols material, can participate in a variety of chemical reactions.By
In having a variety of important physicochemical properties, glycerol is in industries such as coating, salt, medicine, toothpaste, glassine paper, insulating materials
It is occupied an important position in production.For at present, China's glycerol production is constantly in that supply falls short of demand state, especially high-purity
(99.5%) glycerol almost all relies on import.
Glycerol is generally prepared by chemical method or biological fermentation process.Crude oil price rises steadily in recent years, promotes biodiesel
Industry is grown rapidly in the whole world.Biodiesel can generate 10% or so by-product glycerin during the preparation process.It estimates
The yield of the year two thousand twenty whole world glycerol will be up to 41,900,000 liters/year.And these glycerol are a kind of containing certain grease, salt and methanol etc.
Mixture --- it is usually referred to as crude glycerine by we.If crude glycerine is directly entered market, biodiesel can be only reduced
Overall economic efficiency.Therefore, crude glycerine is refined and is of great significance for improving Economic Efficiency of Biodiesel.
According to the energy consumption difference in the purposes and production process of glycerol, under normal circumstances, the purification of glycerol is divided into steaming
Evaporate-decolorizing and refining method, rectifying-decolorizing and refining method, ion exchange-repulsion method for refining.These methods can generate a certain amount of waste residue
And waste water, and height is invested, manufacturing expense is high, and separating technology is mostly cumbersome and energy consumption is larger.If glycerol is used as food-grade or medicine
No matter grade reagent uses any refining methd, it is necessary to just can guarantee that glycerol meets quality mark by ion-exchange process
Standard, high production cost, complex process.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of simple processes, refining crude glycerin method at low cost.
To solve the above-mentioned problems, the present invention proposes following technical scheme:
A kind of method of refining crude glycerin, comprising the following steps:
Crude glycerine generally passes through some simple pretreatments, desalination removal of impurities etc..
Tert-butyl donor, crude glycerine are pressed the mass ratio of the material 1-10:1 by S1, are carried out under solid acid catalyst effect into ether
Then reaction obtains glycerol tertbutyl ether by vacuum distillation；
Glycerol tertbutyl ether is carried out cracking reaction under solid acid catalyst catalysis and obtains glycerol by S2, and the glycerol is used
After methanol dilution, efflux is obtained by filter membrane；
Emathlite is added into the efflux and obtains mixture by S3, and the Emathlite is the 2- of mixture quality
3%, be sufficiently stirred, filter, then filtrate is distilled again, be concentrated after obtain high-purity glycerol；
Wherein, the solid acid catalyst is resin acid catalyst or the immobilized acid catalyst of carrier.
Further technical solution is for it, and the tert-butyl donor includes pure isobutene, liquefied petroleum gas, methyl tertbutyl
At least one of ether, ethyl tert-butyl ether (ETBE), tert-butyl alcohol, the isobutene content in the liquefied natural gas are greater than 15%.
Further technical solution is for it, and the cracking reaction temperature in the step S2 is 90-180 DEG C.
Further technical solution is for it, and in the step S1 is 25-80 DEG C at ether reaction temperature.
Further technical solution is for it, and the mass ratio of methanol and glycerol in the step S2 is 1:1-15.
Further technical solution is for it, and the product of the cracking reaction of the step S2 further includes isobutene, the isobutyl
Alkene, which can recycle, to be recycled in step S1 as tert-butyl donor.
Further technical solution is for it, and whipping temp is 25-100 DEG C in the step S3.
Further technical solution is for it, and the acid resin catalyst or the immobilized acid catalyst of carrier include: alkyl
Substituted benzene sulfonic acid, alkyl-substituted naphthalene sulfonic acids, non-alkyl-substituted benzene sulfonic acid, non-alkyl-substituted naphthalene sulfonic acids, polysulfonate acid type
Resin, poly- perfluorosulfonic acid type resin, heteropoly acid and heteropolyacid salt, molecular sieve, acidic ion liquid, single complex carrier
SO4 2-/MXOYSolid super-strong acid, S2O8 2-/MXOYAt least one of solid super-strong acid, wherein MXOYFor NiO, TiO2, ZrO2,
SiO2, SnO2, Fe2O3, Al2O3, WO3And MoO3At least one of.
Compared with prior art, the accessible technical effect of the present invention includes:
1) present invention obtains the glycerol of purification using chemical method, and the neutralization in traditional separating technology, centrifugation, multistage is avoided to steam
Evaporate/rectifying and etc., simple process；
2) cracking reaction of step S2, temperature is low, and energy consumption is small, and the glycerol purity is high generated via cracking will not introduce it
His impurity；
3) be conducive to catalyst using acid resin catalyst or solid acid catalyst to separate with glycerol, under cracking temperature
It is able to maintain compared with high reaction activity, and is less likely to occur to be carbonized；Obtained glycerol color is reacted in light yellow clear shape, rear place
Reason is simple；
4) pyrolysis product in step S2 further includes isobutene, can be used as the tert-butyl donor of S1 so that isobutene circulation benefit
With substantially reducing production cost.
Specific embodiment
The technical solution in embodiment will be clearly and completely described below.
It should be appreciated that ought use in this specification and in the appended claims, term " includes " and "comprising" instruction
Described feature, entirety, step, operation, the presence of element and/or component, but one or more of the other feature, whole is not precluded
Body, step, operation, the presence or addition of element, component and/or its set.
It is also understood that in this embodiment of the present invention term used in the description merely for the sake of description particular implementation
Example purpose and be not intended to limit the embodiment of the present invention.Such as the institute in specification and appended book of the embodiment of the present invention
As use, other situations unless the context is clearly specified, otherwise " one " of singular, "one" and "the" are intended to wrap
Include plural form.
A kind of method that the embodiment of the present invention proposes refining crude glycerin, comprising the following steps:
Tert-butyl donor, crude glycerine are pressed the ratio 1-10:1 of amount of substance by S1, are carried out under solid acid catalyst catalysis into ether
Reaction, temperature are 25-80 DEG C, to fully reacting, obtain glycerol tertbutyl ether through vacuum distillation；
Glycerol tertbutyl ether is carried out cracking reaction under solid acid catalyst catalysis and obtains glycerol by S2, and reaction temperature is
90-180 DEG C, to fully reacting, after the glycerol methanol dilution, efflux is obtained by filter membrane, the methanol of dilution and
The mass ratio of glycerol is 1:1-15；
Enough Emathlites are added into the efflux and obtain mixture by S3, and the Emathlite is mixture quality
2-3%, be sufficiently stirred, whipping temp be 25-100 DEG C, filtering, it is sweet that high-purity is obtained after being distilled, being concentrated to filtrate
Oil；
Wherein, the solid acid catalyst is acid resin catalyst or the immobilized acid catalyst of carrier.
In specific implementation, the acid resin catalyst or the immobilized acid catalyst of carrier include alkyl-substituted benzene sulphur
Sour, alkyl-substituted naphthalene sulfonic acids, non-alkyl-substituted benzene sulfonic acid, non-alkyl-substituted naphthalene sulfonic acids, poly- sulfonic resin, poly- perfluor
Sulfonic resin, heteropoly acid and heteropolyacid salt, molecular sieve, acidic ion liquid, single complex carrier SO4 2-/MXOYSolid is super
Strong acid, S2O8 2-/MXOYAt least one of solid super-strong acid, wherein MXOYFor NiO, TiO2, ZrO2, SiO2, SnO2, Fe2O3,
Al2O3, WO3And MoO3At least one of.
In specific implementation, the tert-butyl donor includes isobutene, liquefied natural gas, the tertiary fourth of methyl tertiary butyl ether(MTBE), ethyl
At least one of base ether, tert-butyl alcohol, the isobutene content in the liquefied natural gas are greater than 15%.
Such as:
In one embodiment, the tert-butyl donor is methyl tertiary butyl ether(MTBE) and ethyl tert-butyl ether (ETBE).
In one embodiment, the tert-butyl donor is isobutene.
In one embodiment, the tert-butyl donor is the liquefied natural gas containing 15% or more isobutene.
In one embodiment, the tert-butyl donor is the tert-butyl alcohol.
In specific implementation, the product of the cracking reaction of the step S2 further includes isobutene, the isobutene that step S2 is obtained
It can be used as the raw material reacted in step S1 at ether.Circular response is carried out using obtained isobutene as the raw material reacted at ether, from
And the utilization rate of raw material is improved, further decrease production cost.
The cracking reaction of step S2, temperature are 90-180 DEG C, and energy consumption is small, and the glycerol purity is high generated via cracking, no
Other impurities can be introduced, it is at low cost.For example,
In one embodiment, the cracking reaction temperature of step S2 is 180 DEG C.
In one embodiment, the cracking reaction temperature of step S2 is 150 DEG C.
In one embodiment, the cracking reaction temperature of step S2 is 130 DEG C.
It should be noted that being stirred after Emathlite is added in step S3, improving whipping temp can speed up glycerol
Decoloration, improve the quality of glycerol.
Specific embodiment presented below:
Case study on implementation 1,
250g crude glycerine and 25gA15 resin catalyst are added in 1000mL round-bottomed flask, is heated to 75 DEG C, it is slowly logical
Enter 410 grams of isobutene gas, the reaction was continued at 75 DEG C 8 hours.It is down to room temperature to temperature, unreacted isobutene is recycled, filters out
Catalyst obtains glycerol tertbutyl ether through vacuum distillation.
Glycerol tertbutyl ether is transferred to cracking reaction kettle, and catalyst for cracking A15 resin catalyst 25g is added, and reaction temperature is
It 110 DEG C, reacts 2 hours, is down to room temperature, the isobutene that recycling cracking obtains filters out catalyst, obtained glycerol phase homogenous quantities
Methanol dilution, efflux is obtained by filter membrane, into efflux be added qualities of glycerin 2% Emathlite, stirred at 90 DEG C
It mixes 2 hours, then filters Emathlite, high-purity glycerol is obtained after air-distillation steams methanol to filtrate.
By gas chromatographic analysis, glycerol content is about 96.2%, and product is colourless transparent liquid.
Case study on implementation 2,
500g crude glycerine, methyl tertiary butyl ether(MTBE) 383g and 25g A35 resin catalyst are added in 1000mL round-bottomed flask
It carries out into ether to react, is heated to 80 DEG C, and the reaction was continued 8 hours at 80 DEG C.It is down to room temperature to temperature, recycling cracks and end reaction
Isobutene, filter out catalyst, through vacuum distillation obtain glycerol tertbutyl ether.
Glycerol tertbutyl ether is transferred to cracking reaction kettle, and 25g catalyst for cracking SO is added3H-MCM-41, reaction temperature 90
DEG C, it reacts 4 hours, is down to room temperature, the isobutene that recycling cracking obtains filters out catalyst, 0.5 times of quality of obtained glycerol
Methanol dilution obtains efflux by filter membrane, and the Emathlite of qualities of glycerin 3% is added into efflux, stirs 2 at 80 DEG C
Hour, then Emathlite is filtered, high-purity glycerol is obtained after air-distillation steams methanol to filtrate.
By gas chromatographic analysis, glycerol content is about 93.4%, and product is pale yellow transparent liquid.
Case study on implementation 3,
500g crude glycerine, the tert-butyl alcohol 643g and 35g SO are added in 1000mL round-bottomed flask4 2-/SiO2Resin catalyst
It carries out into ether to react, is heated to 70 DEG C, and the reaction was continued 20 hours at 70 DEG C.It is down to room temperature to temperature, recycling cracks and end is anti-
The isobutene answered, filters out catalyst, obtains glycerol tertbutyl ether through vacuum distillation.
Glycerol tertbutyl ether is transferred to cracking reaction kettle, and 25g catalyst for cracking SO is added4 2-/ZrO2-MnO3, reaction temperature is
It 90 DEG C, reacts 4 hours, is down to room temperature, the isobutene that recycling cracking obtains filters out catalyst, 0.2 times of quality of obtained glycerol
Methanol dilution, efflux is obtained by filter membrane, into efflux be added qualities of glycerin 3% Emathlite, stirred at 80 DEG C
It mixes 2 hours, then filters Emathlite, high-purity glycerol is obtained after air-distillation steams methanol to filtrate.
By gas chromatographic analysis, glycerol content is about 99.1%, and product is colourless transparent liquid.
Case study on implementation 4,
500g crude glycerine and 35g SO are added in 1000mL round-bottomed flask4 2-/TiO2Resin catalyst is heated to 70
DEG C, it is passed through liquefied petroleum gas (isobutene content 20%, the amount that control isobutene is passed through substance is 2 times of glycerol), and at 70 DEG C
The reaction was continued 10 hours.It is down to room temperature to temperature, liquefied petroleum gas is recycled, filters out catalyst, obtains glycerol uncle through vacuum distillation
Butyl ether.
Glycerol tertbutyl ether is transferred to cracking reaction kettle, and 25g catalyst for cracking SO is added4 2-/ZrO2-MnO3, reaction temperature is
It 120 DEG C, reacts 1.5 hours, is down to room temperature, the isobutene that recycling cracking obtains filters out catalyst, obtained glycerol Xiang Tongzhi
The methanol dilution of amount simultaneously obtains efflux by filter membrane, the Emathlite of qualities of glycerin 3% is added into efflux, at 60 DEG C
Stirring 2 hours, Emathlite is then filtered, obtain high-purity glycerol after air-distillation steams methanol to filtrate.
By gas chromatographic analysis, glycerol content is about 98.6%, and product is colourless transparent liquid.
The high-purity glycerol that the refining crude glycerin method provided through the embodiment of the present invention obtains has application neck below
Domain: in terms of medicine, to produce various preparations, solvent, hygroscopic agent, antifreezing agent and sweetener, ingredients externally-applied ointment or suppository
Deng；To produce various alkyd resins, polyester resin, glycidol ether and epoxy resin etc. in coatings industry；Weaving and
To produce lubricant, hygroscopic agent, crease-proofing textiles containing contracting inorganic agent, diffusant and bleeding agent in printing and dyeing industry；In the food industry
As the hygroscopic agent in sweetener, tobacco；Antifreezing agent etc. as automobile and aircraft fuel and oil field, papermaking, cosmetics,
Extensive purposes is suffered from the industry such as process hides, photograph, printing, intermetallic composite coating, electrical material and rubber.
In the above-described embodiments, it all emphasizes particularly on different fields to the description of each embodiment, is not described in some embodiment
Part, reference can be made to the related descriptions of other embodiments.
The above is a specific embodiment of the invention, but scope of protection of the present invention is not limited thereto, any ripe
It knows those skilled in the art in the technical scope disclosed by the present invention, various equivalent modifications can be readily occurred in or replaces
It changes, these modifications or substitutions should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with right
It is required that protection scope subject to.
Claims (8)
1. a kind of method of refining crude glycerin, which comprises the following steps:
Tert-butyl donor, crude glycerine are pressed the ratio 1-10:1 of amount of substance by S1, react at ether under solid acid catalyst catalysis,
To fully reacting, glycerol tertbutyl ether is obtained through vacuum distillation；
Glycerol tertbutyl ether is carried out cracking reaction under solid acid catalyst catalysis and obtains glycerol by S2, by the glycerol methanol
After dilution, efflux is obtained by filter membrane；
Emathlite is added into the efflux and obtains mixture by S3, and the Emathlite is the 2-3% of mixture quality, fills
Point stirring, filtering, filtrate is distilled, be concentrated after obtain high-purity glycerol；
Wherein, the solid acid catalyst is acid resin catalyst or the immobilized acid catalyst of carrier.
2. the method for refining crude glycerin according to claim 1, which is characterized in that the tertbutyl ether donor includes pure different
Butylene, liquefied natural gas, the tert-butyl alcohol, methyl tertiary butyl ether(MTBE), at least one of ethyl tert-butyl ether (ETBE), in the liquefied natural gas
Isobutene content be greater than 15%.
3. the method for refining crude glycerin according to claim 1, which is characterized in that react temperature at ether in the step S1
Degree is 25-80 DEG C.
4. the method for refining crude glycerin according to claim 1, which is characterized in that the cracking reaction temperature in the step S2
Degree is 90-180 DEG C.
5. the method for refining crude glycerin according to claim 1, which is characterized in that methanol and glycerol in the step S2
Mass ratio be 1:1-15.
6. the method for refining crude glycerin according to claim 5, which is characterized in that the production of cracking reaction in the step S2
Object further includes isobutene, and the isobutene, which can recycle, to be recycled in step S1 as tert-butyl donor.
7. the method for refining crude glycerin according to claim 1, which is characterized in that whipping temp is in the step S3
25-100℃。
8. the method for refining crude glycerin according to claim 1, which is characterized in that the acid resin catalyst or carrier
Immobilized acid catalyst includes alkyl-substituted benzene sulfonic acid, alkyl-substituted naphthalene sulfonic acids, non-alkyl-substituted benzene sulfonic acid, non-alkyl
Substituted naphthalene sulfonic acids, poly- sulfonic resin, poly- perfluorosulfonic acid type resin, heteropoly acid and heteropolyacid salt, molecular sieve, acidic ionic liquid
The SO of body, single complex carrier4 2-/MXOYSolid super-strong acid, S2O8 2-/MXOYAt least one of solid super-strong acid, wherein MXOY
For NiO, TiO2, ZrO2, SiO2, SnO2, Fe2O3, Al2O3, WO3And MoO3At least one of.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111517921A (en) * | 2020-04-28 | 2020-08-11 | 深圳市前海博扬研究院有限公司 | Process and device for refining glycerol |
| CN113754519A (en) * | 2021-08-11 | 2021-12-07 | 东南大学 | Method for preparing tert-butyl glyceryl ether by using solid acid catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105175203A (en) * | 2015-09-08 | 2015-12-23 | 山东成泰化工有限公司 | Method for preparing isobutene by MTBE (Methyl Tertiary Butyl Ether) |
| CN107056584A (en) * | 2016-12-14 | 2017-08-18 | 天长市康宁甘油科技有限公司 | A kind of method of use refining crude glycerin pharmaceutical grade glycerine |
| CN107207389A (en) * | 2015-01-30 | 2017-09-26 | 沙特基础工业全球技术有限公司 | Method for preparing glycerine tertbutyl ether |
-
2019
- 2019-05-08 CN CN201910380771.0A patent/CN110078591A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107207389A (en) * | 2015-01-30 | 2017-09-26 | 沙特基础工业全球技术有限公司 | Method for preparing glycerine tertbutyl ether |
| CN105175203A (en) * | 2015-09-08 | 2015-12-23 | 山东成泰化工有限公司 | Method for preparing isobutene by MTBE (Methyl Tertiary Butyl Ether) |
| CN107056584A (en) * | 2016-12-14 | 2017-08-18 | 天长市康宁甘油科技有限公司 | A kind of method of use refining crude glycerin pharmaceutical grade glycerine |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111517921A (en) * | 2020-04-28 | 2020-08-11 | 深圳市前海博扬研究院有限公司 | Process and device for refining glycerol |
| CN113754519A (en) * | 2021-08-11 | 2021-12-07 | 东南大学 | Method for preparing tert-butyl glyceryl ether by using solid acid catalyst |
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Application publication date: 20190802 |