CN1763061A - Method for removing chlorhydric acid and ferrous chloride from hydrolysed biomass glyc solution by diluted acid - Google Patents
Method for removing chlorhydric acid and ferrous chloride from hydrolysed biomass glyc solution by diluted acid Download PDFInfo
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- CN1763061A CN1763061A CNA2005100252291A CN200510025229A CN1763061A CN 1763061 A CN1763061 A CN 1763061A CN A2005100252291 A CNA2005100252291 A CN A2005100252291A CN 200510025229 A CN200510025229 A CN 200510025229A CN 1763061 A CN1763061 A CN 1763061A
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Abstract
The process of eliminating hydrochloric acid and ferrous chloride from saccharide solution obtained via hydrolyzing biomass with dilute acid includes the following steps: making the saccharide solution pass through the first anionic exchange column, the cationic exchange column and the second anionic exchange column successively to eliminate hydrochloric acid and ferrous chloride. The present invention has simple operation, low processing cost and probability of recovering and reusing ferrous chloride. The present invention has ultimate solution pH 5.6 and ferrous chloride concentration lower than 0.00194 kmol/cu m.
Description
Technical field
The present invention relates to a kind of from containing HCl and FeCl
2Solution in remove the method for these two kinds of materials, particularly a kind ofly behind the biomass dilute acid hydrolysis, the liquid glucose of gained, remove HCl and FeCl with series connection ion exchange column method
2Method.
Technical background
Along with petering out and the continuous rise of International Crude Oil of the non-renewable fossil class energy, the development and use aboundresources, can not cause the biomass energy of environmental pollution to have the important strategic meaning.
Biomass are not only originated abundant, and are unique renewable resourcess that is converted into liquid fuel.It absorbs the CO in the atmosphere in process of growth
2, can alleviate the environmental problem and the Greenhouse effect that use fossil oil to bring.Under this background, the exploitation of biomass waste preparing liquid fuel technology has been subjected to paying attention to widely, and this centre has industrial prospect most with the technology of lignocellulose dilute acid hydrolysis producing fuel alcohol again.
Contain a large amount of Mierocrystalline celluloses and hemicellulose in the biomass material, can obtain monose after with its hydrolysis, can obtain fuel alcohol to the monose fermentation again with diluted acid.
Dilute acid hydrolysis is generally used mineral acid, and commonly used is sulfuric acid or hydrochloric acid.The price of hydrochloric acid is higher, but hydrolysis efficiency is better than sulfuric acid, when cheap dilute hydrochloric acid source is arranged, can consider to use it for hydrolysis.
In order to improve the efficient of dilute acid hydrolysis, available some inorganic salt are (as FeCl
3And FeCl
2Deng) make promotor, further promote the katalysis of acid.East China University of Science has developed with HCl-FeCl
2Be the dilute acid hydrolysis process of catalyzer, FeCl
2The higher catalytic capability that helps is not only arranged, and cheap, just can produce easily with abraum salt acid and iron filings, very favourable to industrialization.
HCl-FeCl
2Though be used for dilute acid hydrolysis very high efficient is arranged, also exist the problem of aftertreatment difficulty.Traditional method is with sodium hydroxide or calcium hydroxide neutralization, its pH value is adjusted to the scope (pH=5-6) that is fit to fermentation hydrolyzed solution.But NaCl and CaCl
2Solubleness all very big, can't remove with the precipitator method, this cause injurious effects will for follow-up fermentation workshop section, reduces the zymic fermentation efficiency.
Summary of the invention
The technical issues that need to address of the present invention provide and a kind ofly remove HCl and FeCl from biomass dilute acid hydrolysis liquid glucose
2Method, to solve the defective that prior art exists.
Design of the present invention:
In the technology of biomass dilute acid hydrolysis fermentation preparing alcohol, if method that can be by ion-exchange hydrolysis after HCl and FeCl in the gained liquid glucose
2Remove, then not only help next step liquid glucose fermentation; And because of saltiness in the waste liquid that produces after the fermented liquid rectifying is very low, but reuse after biochemical treatment.During with HCl solution cation regenerant resin, can obtain the FeCl of certain acidity
2Solution, after handling a little, this solution just can be used as catalyzer and uses.NaCl in the salts solution that resin anion(R.A) regeneration is produced is dense, do after recyclable industrial, but remaining also reuse of water.So just solved the pollution problem that the brine waste discharging causes in the dilute acid hydrolysis process, very favourable to environmental protection.But, remove Fe by resin cation exchange because of hydrolyzed solution has stronger acidity
2+, must reduce earlier the acidity of solution, but prevent to cause Fe (OH) again because of acidity is low excessively
2Precipitation.The present invention adopts with series connection ion exchange column technology and removes HCl and FeCl for this reason
2Method.When with the lower concentration acid hydrolysis, running cost is also lower.
Method of the present invention comprises the steps:
(in the gross weight of liquid glucose, sugared content is 3～10% to the liquid glucose that biomass are obtained through dilute acid hydrolysis, and HCl is 0.3-3%, FeCl
2Being 0.2-2%, acidity is＜pH=0.3) successively by first anion-exchange column, cationic exchange coloum and second anion-exchange column, to remove hydrochloric acid and the iron protochloride in the hydrolysis sugar liquid; The pH value of final solution can reach 5.6, FeCl
2Concentration can be reduced to 0.00187kmol/m
3Below.
The solution acidity that goes out first anion-exchange column significantly reduces than original solution, and solution acidity is≤pH=2 to keep certain acidity, so that no ferric hydroxide precipitate produces on the cationic exchange coloum;
Solution during by this 3 exchange columns empty scope be 1.5-15min.
Saidly can adopt following formula to express when empty:
V1/V
Wherein: V is the liquid glucose volume that enters ion exchange column the unit time;
V1 is the resin volume that ion exchange column filling;
It is D315 or D301 anionite-exchange resin that the resin that said first anion-exchange column and second anion-exchange column adopt is selected from the trade mark, can adopt the commercially available prod, as the product of East China University Of Science And Technology Huachang Polymer Co., Ltd;
It is 732 or the Zeo-karb of DK110 that the resin that cationic exchange coloum adopts is selected from the trade mark, can adopt the commercially available prod, as the product of East China University Of Science And Technology Huachang Polymer Co., Ltd;
The saturated back of first anion-exchange column and second anion-exchange column is with containing 1kmol/m
3The regeneration of the solution of sodium hydroxide and 0-3kmol/m3 sodium-chlor, alkali lye are undertaken by the method for production of resins merchant regulation during by anion-exchange column empty.Regeneration after cationic exchange coloum is saturated is undertaken by the method for production of resins merchant regulation, can produce the solution of ferrous chloride of certain acidity in the regenerative process, and this solution can be used as catalyzer and uses.
The acidity and the iron protochloride that adopt method of the present invention to handle back solution all can satisfy the requirement of the follow-up workshop section of fermenting.The saturated back of cationic exchange coloum can be used as catalyzer and uses with hydrochloric acid soln regeneration, the solution of ferrous chloride that obtains certain acidity.Regenerates with containing sodium hydroxide solution in the saturated back of first anion-exchange column and second anion-exchange column, sodium hydroxide constantly is converted into sodium-chlor in the regenerative process, at this moment can be in alkali lye the hydrogen make-up sodium oxide, make its concentration remain on 1kmol/m
3About.Last this alkali lye is converted into the sodium chloride solution of high density, can be industrial with doing after its recovery, but remaining also reuse of water.Present method not only can make the salt concn in the biomass dilute acid hydrolysis gained liquid glucose significantly reduce, and helps follow-up fermentation; But and the reuse after biochemical treatment of the waste liquid after the rectifying.This has just solved the pollution problem that the brine waste discharging causes in the dilute acid hydrolysis process.
This shows, method of the present invention, easy and simple to handle, processing cost is lower, can recycle solution of ferrous chloride wherein, and is suitable to circulate.The present invention has tangible economic benefit and social benefit.The pH value of final solution is 5.6, FeCl
2Concentration can be reduced to 0.00187kmol/m
3
Embodiment
The invention will be further described below by several examples, but this does not influence protection scope of the present invention
Embodiment 1
Be filled with the fresh anionite-exchange resin D315 of 100ml in first anion column, be filled with the fresh anionite-exchange resin D315 of 100ml in second anion column, be filled with the fresh Zeo-karb of 100mll 732 in the cation seperation column.
Resin provides by East China University Of Science And Technology Huachang Polymer Co., Ltd.Here and the resin volume of hereinafter mentioning be apparent volume.
Get 500ml and contain 2%HCl, 2%FeCl
2With the solution of 3% glucose, under normal pressure and 20 ℃, make it successively by first anion column, cation seperation column and second anion column.Wherein by the first anion column time spent 10min, by cation seperation column time spent 10min, by the second anion column time spent 10min.
The solution acidity that goes out first anion-exchange column is pH=2
The pH value of measuring final solution is 5.0, FeCl
2Concentration be 0.00364kmol/m
3
Embodiment 2
First anion column, the resin kind and the loadings of loading in second anion column and the cation seperation column all are equal to embodiment 1.
Get 500ml and contain 2%HCl, 0.5%FeCl
2With the solution of 3% glucose, under normal pressure and 20 ℃, make it successively by first anion column, cation seperation column and second anion column.Wherein by the first anion column time spent 10min, by cation seperation column time spent 5min, by the second anion column time spent 10min.
The solution acidity that goes out first anion-exchange column is pH=2
The pH value of measuring final solution is 5.6, FeCl
2Concentration be 0.00187kmol/m
3
Embodiment 3
First anion column, the resin kind and the loadings of loading in second anion column and the cation seperation column all are equal to embodiment 1.But the resin anion(R.A) that first anion column and second anion column are loaded is a saturated back regenerated, and what use during regeneration is to contain 1kmol/m
3Sodium hydroxide and 3kmol/m
3The solution of sodium-chlor.The resin cation (R.C.) that cationic exchange coloum loaded is to use 1kmol/m after saturated
3The hydrochloric acid soln regenerated.
Get 500ml and contain 2%HCl, 0.5%FeCl
2With the solution of 3% glucose, under normal pressure and 20 ℃, make it successively by first anion column, cation seperation column and second anion column.Wherein by the first anion column time spent 10min, by cation seperation column time spent 5min, by the second anion column time spent 10min.
The solution acidity that goes out first anion-exchange column is controlled at pH=2
The pH value of measuring final solution is 5.6, FeCl
2Concentration be 0.00194kmol/m
3
Claims (6)
1. the removal methods of hydrochloric acid and iron protochloride in the biomass dilute acid hydrolysis liquid glucose, it is characterized in that, comprise the steps: biomass are passed through first anion-exchange column, cationic exchange coloum and second anion-exchange column successively through the liquid glucose that dilute acid hydrolysis obtains, can remove hydrochloric acid and iron protochloride in the hydrolysis sugar liquid.
2. method according to claim 1 is characterized in that, in the liquid glucose, the weight content of sugar is 3～10%, and the weight content of HCl is 0.3-3%, the FeCl that weight content is
20.2-2%, acidity is＜pH=0.3.
3. method according to claim 1 is characterized in that, the solution acidity that goes out first anion-exchange column is≤pH=2.
4. method according to claim 1 is characterized in that, solution during by three exchange columns empty scope be 1.5-15min.
5. method according to claim 1 is characterized in that, the saturated back of first anion-exchange column and second anion-exchange column is with containing 1kmol/m
3Sodium hydroxide and 0-3kmol/m
3The solution regeneration of sodium-chlor.
6. method according to claim 1, it is characterized in that, the resin that said first anion-exchange column and second anion-exchange column adopt is selected from the anionite-exchange resin that the trade mark is D315 or D301, and it is 732 or the Zeo-karb of DK110 that the resin that cationic exchange coloum adopts is selected from the trade mark.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100252291A CN1331875C (en) | 2005-04-20 | 2005-04-20 | Method for removing chlorhydric acid and ferrous chloride from hydrolysed biomass glyc solution by diluted acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100252291A CN1331875C (en) | 2005-04-20 | 2005-04-20 | Method for removing chlorhydric acid and ferrous chloride from hydrolysed biomass glyc solution by diluted acid |
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| Publication Number | Publication Date |
|---|---|
| CN1763061A true CN1763061A (en) | 2006-04-26 |
| CN1331875C CN1331875C (en) | 2007-08-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100252291A Expired - Fee Related CN1331875C (en) | 2005-04-20 | 2005-04-20 | Method for removing chlorhydric acid and ferrous chloride from hydrolysed biomass glyc solution by diluted acid |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775447B (en) * | 2010-01-27 | 2012-07-18 | 中国农业大学 | Method for preprocessing biomass raw material by electrolyzed water ionic system |
| CN106632525A (en) * | 2016-12-27 | 2017-05-10 | 厦门欣赛科技有限公司 | Method for separating sulfuric acid from a glucose-xylose solution |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1199976C (en) * | 2003-07-03 | 2005-05-04 | 华东理工大学 | Electrodialysis method for separating sugar and acid in biomass hydrolysate |
-
2005
- 2005-04-20 CN CNB2005100252291A patent/CN1331875C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775447B (en) * | 2010-01-27 | 2012-07-18 | 中国农业大学 | Method for preprocessing biomass raw material by electrolyzed water ionic system |
| CN106632525A (en) * | 2016-12-27 | 2017-05-10 | 厦门欣赛科技有限公司 | Method for separating sulfuric acid from a glucose-xylose solution |
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|---|---|
| CN1331875C (en) | 2007-08-15 |
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