CN107382696A - A kind of method that pulping waste liquor oxidation prepares acetic acid - Google Patents
A kind of method that pulping waste liquor oxidation prepares acetic acid Download PDFInfo
- Publication number
- CN107382696A CN107382696A CN201710617891.9A CN201710617891A CN107382696A CN 107382696 A CN107382696 A CN 107382696A CN 201710617891 A CN201710617891 A CN 201710617891A CN 107382696 A CN107382696 A CN 107382696A
- Authority
- CN
- China
- Prior art keywords
- waste liquor
- pulping waste
- acetic acid
- filtrate
- pulping
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method that pulping waste liquor oxidation prepares acetic acid, comprise the following steps：(1) by string after boiling, carry out separation of solid and liquid and obtain pulping waste liquor and waste liquid；(2) after above-mentioned pulping waste liquor is mixed with sodium hydroxide and oxidant, it is placed in autoclave, is heated to 140~250 DEG C of 2~60min of reaction；(3) reaction product obtained by step (2) is obtained into filtrate through centrifuging, washing and filter；(4) above-mentioned filtrate is subjected to acidification with 10~75% sulfuric acid, then purified through being evaporated under reduced pressure, obtain purpose product acetic acid.Technical scheme is easy and effective, and waste liquid full constituent can be achieved and utilize, realize zero-emission target.
Description
Technical field
The invention belongs to pulping waste liquor processing technology field, and in particular to a kind of pulping waste liquor oxidation prepares the side of acetic acid
Method.
Background technology
In recent years, with the increasingly depleted of fossil resource and becoming increasingly conspicuous for environmental problem, green low-carbon idea of development is not
Disconnected to be rooted in the hearts of the people, the biorefinery technology utilized with biomass full constituent turns into the field newly developed to get most of the attention, tradition system
Slurry paper technology faces huge challenge, and new preprocess method and pulping by cooking technology is continued to bring out, and pulping waste liquor is progressively returned
Receive and utilize.Patent CN105332309A discloses a kind of from solid base pulping waste liquor separated in synchronization lignin and recovery solid base
Method, the alkali recovery and lignin yield of this method are higher, and operating procedure is simple, effectively prevent pulping cooking waste liquor
Be difficult by, alkali collection complex procedures the shortcomings of, significantly reduce the cost of pulping by cooking solid base, but this method does not have
Soluble component in waste liquid is effectively utilized.
The content of the invention
It is an object of the invention to overcome prior art defect, there is provided a kind of method that pulping waste liquor oxidation prepares acetic acid.
Technical scheme is as follows：
A kind of method that pulping waste liquor oxidation prepares acetic acid, it is characterised in that：Comprise the following steps：
(1) by string after boiling, carry out separation of solid and liquid and obtain paper pulp and pulping waste liquor；
(2) after mixing above-mentioned pulping waste liquor sodium hydroxide and oxidant, it is placed in autoclave, it is heated to 140~
250 DEG C of 2~60min of reaction；
(3) reaction product obtained by step (2) is obtained into filtrate through centrifuging, washing and filter；
(4) above-mentioned filtrate is subjected to acidification with 10~75% sulfuric acid, then purified through being evaporated under reduced pressure, obtain purpose production
Thing acetic acid.
In a preferred embodiment of the invention, the oxidant is oxygen.
It is further preferred that the mass ratio of the pulping waste liquor and sodium hydroxide is 50: 2, the amount of the oxygen of addition is to take
For the gas in autoclave and the pressure in autoclave is set to reach 3MPa.
In a preferred embodiment of the invention, the oxidant is 30% hydrogen peroxide.
It is further preferred that the mass ratio of the pulping waste liquor, sodium hydroxide and 30% hydrogen peroxide is 20: 2~2.8: 30
~50, and concentration of the sodium hydroxide in pulping waste liquor and 30% hydrogen peroxide is 0.8~1.2mol/L.
In a preferred embodiment of the invention, the temperature in the step (2) is 150~240 DEG C.
Beneficial effects of the present invention：Technical scheme is easy and effective, and waste liquid full constituent can be achieved and utilize, realize zero
Emissions object.
Embodiment
Technical scheme is further detailed and described below by way of embodiment.
By string after boiling, carry out separation of solid and liquid and obtain paper pulp and the pulping waste liquor used in following embodiments.
Embodiment 1
50.00g pulping waste liquors are added in 100mL autoclaves, 2.00g sodium hydroxides, are gone out with replacement of oxygen in kettle
Air and oxygenation to pressure in kettle are 3MPa, and reaction temperature is 240 DEG C, reaction time 30min.After reaction terminates, by gained
Reaction product through centrifuging, wash and filter, obtain filtrate, take the sulfuric acid that 2~3mL mass fractions are 12% to be acidified, dilution 10
Qualitative detection is carried out to purpose product with HPLC after times, then quantitative calculating is carried out with mark song, the quality for measuring acetic acid in filtrate is dense
Spend for 2.07mg/g, the yield relative to biomass material is 8.28%.
Embodiment 2
50.00g pulping waste liquors are added in 100mL autoclaves, 2.00g sodium hydroxides, are gone out with replacement of oxygen in kettle
Air and oxygenation to pressure in kettle are 3MPa, and reaction temperature is 240 DEG C, reaction time 20min.After reaction terminates, by gained
Reaction product through centrifuging, wash and filter, obtain filtrate, take the sulfuric acid that 2~3mL mass fractions are 12% to be acidified, dilution 10
Qualitative detection is carried out to purpose product with HPLC after times, then quantitative calculating is carried out with mark song, the quality for measuring acetic acid in filtrate is dense
Spend for 1.92mg/g, the quality yield relative to biomass material is 7.70%.
Embodiment 3
50.00g pulping waste liquors are added in 100mL autoclaves, 2.00g sodium hydroxides, are gone out with replacement of oxygen in kettle
Air and oxygenation to pressure in kettle are 3MPa, and reaction temperature is 240 DEG C, reaction time 10min.After reaction terminates, by gained
Reaction product through centrifuging, wash and filter, obtain filtrate, take the sulfuric acid that 2~3mL mass fractions are 12% to be acidified, dilution 10
Qualitative detection is carried out to purpose product with HPLC after times, then quantitative calculating is carried out with mark song, the quality for measuring acetic acid in filtrate is dense
Spend for 1.91mg/g, the quality yield relative to biomass material is 7.63%.
Embodiment 4
10.00g pulping waste liquors, 0.40g sodium hydroxides, 200wt% 30% dioxygen are added in 50mL autoclaves
Water, reaction temperature are 240 DEG C, reaction time 30min.After reaction terminates, by the reaction product of gained through centrifuging, wash and
Filtering, obtains filtrate, takes the sulfuric acid that 2~3mL mass fractions are 72% to be acidified, purpose product is entered with HPLC after 10 times of dilution
Row qualitative detection, then quantitative calculating is carried out with mark song, the mass concentration for measuring acetic acid in filtrate is 2.20mg/g, relative to life
The quality yield of raw material of substance is 8.81%.
Embodiment 5
10.00g pulping waste liquors, 0.40g sodium hydroxides, 200wt% 30% dioxygen are added in 50mL autoclaves
Water, reaction temperature are 240 DEG C, reaction time 20min.After reaction terminates, by the reaction product of gained through centrifuging, wash and
Filtering, obtains filtrate, takes the sulfuric acid that 2~3mL mass fractions are 72% to be acidified, purpose product is entered with HPLC after 10 times of dilution
Row qualitative detection, then quantitative calculating is carried out with mark song, the mass concentration for measuring acetic acid in filtrate is 2.29mg/g, relative to life
The quality yield of raw material of substance is 9.17%.
Embodiment 6
10.00g pulping waste liquors, 0.40g sodium hydroxides, 200wt% 30% dioxygen are added in 50mL autoclaves
Water, reaction temperature are 240 DEG C, reaction time 2min.After reaction terminates, by the reaction product of gained through centrifuging, washing and mistake
Filter, obtains filtrate, takes the sulfuric acid that 2~3mL mass fractions are 72% to be acidified, purpose product is carried out with HPLC after 10 times of dilution
Qualitative detection, then quantitative calculating is carried out with mark song, the mass concentration for measuring acetic acid in filtrate is 2.30mg/g, relative to biology
The quality yield of matter raw material is 9.19%.
Embodiment 7
10.00g pulping waste liquors, 1.20g sodium hydroxides, 200wt% 30% dioxygen are added in 50mL autoclaves
Water, reaction temperature are 240 DEG C, reaction time 2min.After reaction terminates, by the reaction product of gained through centrifuging, washing and mistake
Filter, obtains filtrate, takes the sulfuric acid that 2~3mL mass fractions are 72% to be acidified, purpose product is carried out with HPLC after 10 times of dilution
Qualitative detection, then quantitative calculating is carried out with mark song, the mass concentration for measuring acetic acid in filtrate is 2.31mg/g, relative to biology
The quality yield of matter raw material is 9.24%.
Embodiment 8
20.00g pulping waste liquors, 2.00g sodium hydroxides, 150wt% 30% dioxygen are added in 100mL autoclaves
Water, reaction temperature are 240 DEG C, reaction time 2min.After reaction terminates, by the reaction product of gained through centrifuging, washing and mistake
Filter, obtains filtrate, takes the sulfuric acid that 2~3mL mass fractions are 72% to be acidified, purpose product is carried out with HPLC after 10 times of dilution
Qualitative detection, then quantitative calculating is carried out with mark song, the mass concentration for measuring acetic acid in filtrate is 1.84mg/g, relative to biology
The quality yield of matter raw material is 7.36%.
Embodiment 9
20.00g pulping waste liquors, 2.80g sodium hydroxides, 250wt% 30% dioxygen are added in 100mL autoclaves
Water, reaction temperature are 240 DEG C, reaction time 2min.After reaction terminates, by the reaction product of gained through centrifuging, washing and mistake
Filter, obtains filtrate, takes the sulfuric acid that 2~3mL mass fractions are 72% to be acidified, purpose product is carried out with HPLC after 10 times of dilution
Qualitative detection, then quantitative calculating is carried out with mark song, the mass concentration for measuring acetic acid in filtrate is 3.04mg/g, relative to biology
The quality yield of matter raw material is 10.39%.
The foregoing is only a preferred embodiment of the present invention, therefore can not limit the scope that the present invention is implemented according to this, i.e.,
The equivalent changes and modifications made according to the scope of the claims of the present invention and description, all should still it belong in the range of the present invention covers.
Claims (6)
1. a kind of method that pulping waste liquor oxidation prepares acetic acid, it is characterised in that：Comprise the following steps：
(1) by string after boiling, carry out separation of solid and liquid and obtain paper pulp and pulping waste liquor；
(2) after above-mentioned pulping waste liquor is mixed with sodium hydroxide and oxidant, it is placed in autoclave, is heated to 140~250
DEG C reaction 2~60min；
(3) reaction product obtained by step (2) is obtained into filtrate through centrifuging, washing and filter；
(4) above-mentioned filtrate is subjected to acidification with 10~75% sulfuric acid, then purified through being evaporated under reduced pressure, obtain purpose product second
Acid.
2. the method as described in claim 1, it is characterised in that：The oxidant is oxygen.
3. method as claimed in claim 2, it is characterised in that：The mass ratio of the pulping waste liquor and sodium hydroxide is 50: 2,
The amount of the oxygen of addition is the gas in substitution autoclave and the pressure in autoclave is reached 3MPa.
4. the method as described in claim 1, it is characterised in that：The oxidant is 30% hydrogen peroxide.
5. method as claimed in claim 4, it is characterised in that：The matter of the pulping waste liquor, sodium hydroxide and 30% hydrogen peroxide
Amount is than being 20: 2~2.8: 30~50, and concentration of the sodium hydroxide in pulping waste liquor and 30% hydrogen peroxide is 0.8~1.2mol/
L。
6. the method as described in claim 1, it is characterised in that：Temperature in the step (2) is 150~240 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710617891.9A CN107382696A (en) | 2017-07-26 | 2017-07-26 | A kind of method that pulping waste liquor oxidation prepares acetic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710617891.9A CN107382696A (en) | 2017-07-26 | 2017-07-26 | A kind of method that pulping waste liquor oxidation prepares acetic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107382696A true CN107382696A (en) | 2017-11-24 |
Family
ID=60341556
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710617891.9A Pending CN107382696A (en) | 2017-07-26 | 2017-07-26 | A kind of method that pulping waste liquor oxidation prepares acetic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107382696A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115108903A (en) * | 2022-06-07 | 2022-09-27 | 安徽秸家生物科技开发有限公司 | Method for preparing acetic acid by treating alkalized straw based on one-pot two-step method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1607296A (en) * | 2003-10-13 | 2005-04-20 | 陕西科技大学 | Super critical water oxidation process for soda cooking black liquor |
| CN102561084A (en) * | 2011-12-22 | 2012-07-11 | 江门市慧信净水材料有限公司 | Resource treatment technology for black liquor |
-
2017
- 2017-07-26 CN CN201710617891.9A patent/CN107382696A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1607296A (en) * | 2003-10-13 | 2005-04-20 | 陕西科技大学 | Super critical water oxidation process for soda cooking black liquor |
| CN102561084A (en) * | 2011-12-22 | 2012-07-11 | 江门市慧信净水材料有限公司 | Resource treatment technology for black liquor |
Non-Patent Citations (1)
| Title |
|---|
| Ф.И.郭尔钦金等: "利用硫酸盐法纸浆工业中废液制造醋酸的试验", 《化学世界》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115108903A (en) * | 2022-06-07 | 2022-09-27 | 安徽秸家生物科技开发有限公司 | Method for preparing acetic acid by treating alkalized straw based on one-pot two-step method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8585863B2 (en) | Separation of lignin from hydrolyzate | |
| Jahan et al. | Potassium hydroxide pulping of rice straw in biorefinery initiatives | |
| Abdulkhani et al. | Concurrent production of sodium lignosulfonate and ethanol from bagasse spent liquor | |
| RU2008126769A (en) | CARRYING OUT IN THE CATALYTIC REACTOR THE PROCESS OF PRODUCING INDUSTRIAL CELLULOSE MASS, NATIVE LIGNIN AND SINGLE CELL PROTEIN | |
| CN105330869B (en) | A kind of method for hydrolysis of lignocellulose raw material | |
| CN102604121A (en) | Method for preparing high-quality lignin by coupling hydrothermal pretreatment and high-boiling-point alcohol | |
| CN111979819B (en) | Method for separating lignocellulosic biomass components | |
| CN107324989A (en) | It is a kind of by being dehydrated the method that extraction prepares lactic acid and lactide | |
| CN109706769A (en) | A kind of method that organic acid separation lignocellulosic is blended in small molecule aldehyde organic matter | |
| CN107382696A (en) | A kind of method that pulping waste liquor oxidation prepares acetic acid | |
| CN107937446A (en) | A kind of technique using maize straw as waste ethanol | |
| CN101455291B (en) | Fructose and oligo-fructose production method using garlic fructosan hydrolase | |
| CN105350369B (en) | The preparation technology of the lignocellulosic slurrying pre-hydrolyzed solution with high-efficiency fermenting ability | |
| CN112030591A (en) | Novel method for recycling alkali from straw pulp black liquor by acid-alkali circulation | |
| CN103694101A (en) | Comprehensive utilization method of sodium hydrosulfite waste residue | |
| CN111848976B (en) | Method for preparing lignosulfonate by using dissolving pulp precooking waste liquid and application | |
| CN104178777B (en) | Method for recovering sodium hydroxide by combining lignin extraction from pulping alkaline waste liquid with electrolysis | |
| CN110818770B (en) | Method for preparing diosgenin by ternary biphase aluminum chloride hydrolysis | |
| US20130283795A1 (en) | Process for producing alcohol and other bioproducts from biomass extracts in a kraft pulp mill | |
| CN106674538A (en) | Method for separating and extracting cellulose, degraded hemicellulose and lignin from bamboo wood | |
| CN106397611A (en) | Separation method for two-step-organic-solvent biological-refined ingredients of oil tea processing wastes | |
| US20120237989A1 (en) | Separation of lignin from hydrolyzate | |
| CN111958730B (en) | Method for inhibiting lignin condensation | |
| CN110550797B (en) | Method for efficiently classifying and separating organic matters in pulping yellow liquor | |
| JP2014015439A (en) | Method for producing lignin decomposed product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20171124 |
|
| RJ01 | Rejection of invention patent application after publication |