CN110835185A - Method for separating acid and ester from mixed solution - Google Patents
Method for separating acid and ester from mixed solution Download PDFInfo
- Publication number
- CN110835185A CN110835185A CN201911214041.XA CN201911214041A CN110835185A CN 110835185 A CN110835185 A CN 110835185A CN 201911214041 A CN201911214041 A CN 201911214041A CN 110835185 A CN110835185 A CN 110835185A
- Authority
- CN
- China
- Prior art keywords
- acid
- mixed solution
- ester
- separating
- hydroxide
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
Abstract
The invention belongs to the technical field of membrane separation, and particularly relates to a method for separating acid and ester from a mixed solution; the method comprises the steps of regulating the pH value of a mixed solution to 5-8 by using a pH regulator in the first stage, separating the obtained solution by using a membrane element in the second stage, and respectively collecting trapped liquid and permeate liquid; the mixed solution at least comprises acid and ester; the invention has the beneficial effects that: the method for separating the acid and the ester from the mixed solution is provided, chemical reagents such as a resolving agent, an extracting agent and the like are not needed, the acid and the ester can be effectively separated, the operation is simple, the energy consumption is low, and the method is green and environment-friendly.
Description
Technical Field
The invention belongs to the technical field of membrane separation, and particularly relates to a method for separating acid and ester from a mixed solution.
Background
In fine chemical production or industrial biosynthesis, an intermediate mixture containing acid and ester is often generated, and the acid and the ester in the mixture need to be separated to obtain a target product. In the prior art, two separation methods of acid and ester are adopted, wherein one method is an extraction method, and the other method is a distillation method. The extraction method requires extraction of the mixture with an organic reagent such as ethyl acetate, and separation of the acid and the ester is achieved by utilizing the difference in solubility between the two in immiscible solvents. The method has the following disadvantages: when conventional extraction methods are used to separate acids or esters, organic reagents are required. Commonly used extractants, such as ethyl acetate, are flammable and highly irritating and volatile. In the processes of extraction separation, solvent recovery and other industrial production activities, the use of a large amount of ethyl acetate not only brings potential safety hazards to daily production of factories, but also forms a severe operating environment and brings influences to physical and psychological health of production workers. The distillation method is adopted to realize the separation of the acid and the ester according to the difference of the boiling points of the acid and the ester, and as the distillation equipment has large energy consumption, high cost, higher temperature and larger danger coefficient, under the condition of high temperature, the problems of more reaction side products and lower yield of target products exist.
Disclosure of Invention
The invention aims to provide a method for separating acid and ester from a mixed solution, which has the advantages of simple operation, environment-friendly process and high product purity.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for separating acid and ester from a mixed solution comprises the steps of adjusting the pH of the mixed solution to 5-8 by using a pH regulator in the first stage, separating the obtained solution by using a membrane element in the second stage, and collecting trapped liquid and permeate liquid respectively; the mixed solution at least comprises acid and ester.
The invention has the beneficial effects that: the method for separating the acid and the ester from the mixed solution is provided, chemical reagents such as a resolving agent, an extracting agent and the like are not needed, the acid and the ester can be effectively separated, the operation is simple, the energy consumption is low, and the method is green and environment-friendly.
Detailed Description
The technical solution of the present invention is further described below with reference to examples.
A method for separating acid and ester from a mixed solution comprises the steps of adjusting the pH of the mixed solution to 5-8 by using a pH regulator in the first stage, separating the obtained solution by using a membrane element in the second stage, and respectively collecting trapped liquid and permeate liquid; the mixed solution at least comprises acid and ester.
In the technical scheme, the pH regulator can convert acid in the mixed solution into acid salt, and the separation of the acid and the ester is realized by utilizing the interception performance of the membrane element on metal salt ions. The selection of the type of the pH adjuster and the amount of the pH adjuster used have an important influence on the separation effect. The amount of the pH regulator is realized by monitoring the pH value in the solution, when the pH value is too low, the salting reaction of acid is not sufficient, the separation effect is not obvious, and when the pH value is too high, the excessive use of the pH regulator is reflected, the hydrolysis of partial ester is caused, and the separation effect is also influenced. According to the invention, the pH regulator is selected to regulate the pH of the mixed solution to 5-8, so that the acid can be fully converted into acid salt, the ester is prevented from being hydrolyzed, and full separation and effective separation are ensured. In order to further improve the separation quality and ensure the purity and recovery rate of acid salt and ester, membrane elements can be adopted for repeated separation for many times, the trapped fluid obtained after treatment is acid salt, and the permeate liquid obtained is ester.
Preferably, the pH adjuster is at least one selected from magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, barium oxide, barium hydroxide, ferrous oxide, ferrous hydroxide, ferric oxide, ferric hydroxide, cupric oxide, cupric hydroxide, manganese oxide, and manganese hydroxide.
The form of the pH adjusting agent does not affect the separation process, and in particular, the pH adjusting agent may be a solid or an aqueous solution.
Preferably, the molecular weight cut-off of the membrane element is 200-800D. The membrane element can be a separation device with a nanofiltration membrane.
Preferably, the acid is an organic acid and the ester is an organic acid ester.
Preference is given toThe organic acid has-COOH, -SO attached to the molecule3H. -RSOOH, -RCOSH, said organic acid ester being a lactide or a lactone.
Preferably, the organic acid is at least one of lactic acid, glycolic acid, L-pantoic acid, D-pantoic acid, α -hydroxybutyric acid, β -hydroxybutyric acid and gluconic acid, and the organic acid ester is at least one of glycolide, lactide, valerolactone, D-pantoic lactone, L-pantoic lactone and gluconolactone.
Preferably, the concentration of the acid in the mixed solution is 0.5-999g/L, and the concentration of the ester is 0.5-999 g/L.
Preferably, the solution further comprises a step of removing an impurity component in the mixed solution before the separation by the membrane element.
Preferably, the method for removing impurity components from the mixed solution comprises:
1) carrying out adsorption filtration on the mixed solution, and collecting filtrate; and/or
2) Filtering the mixed solution by adopting a membrane element with the molecular weight cutoff of 1000-10000D, and collecting the permeate; and/or
3) Treating the mixed solution by using a plate separation method, and collecting plate separation clear liquid.
The adsorption filter medium comprises activated carbon and/or diatomite; the membrane element is at least one of a microfiltration membrane, a nanofiltration membrane and an ultrafiltration membrane.
Before the membrane element is adopted to separate the solution, active carbon or diatomite can be added, the adding amount is 0.8-1.2% of the volume of the solution, and the solution is stirred for 0.5-1 hour. The activated carbon or diatomite is added, so that the impurities in the solution can be adsorbed, and the filter aid effect is achieved. The membrane element with the cut-off molecular weight of 1000-10000D is adopted for filtering, so that thalli, macromolecular protein and micromolecular impurities can be removed, and a relatively pure mixed solution of acid salt and ester is obtained.
Example (b):
the enzymatic products in the following examples are: DL pantoic acid lactone is subjected to enzymolysis and conversion by D pantoic acid lactone hydrolase to obtain a mixed solution containing target separation products such as D pantoic acid calcium, L pantoic acid lactone and the like and impurities such as bacteria, protein and the like.
The enzymolysis and transformation method can refer to the microbial enzyme method for preparing D-pantolactone in New Tang of south China university. Specifically, the following steps can be also included: mixing water and DL pantoic acid lactone to prepare DL pantoic acid lactone solution with the concentration of 200g/L, then adding a proper amount of D pantoic acid lactone hydrolase, adjusting the pH of the solution to 6.0-8.0 by using calcium salt, converting for 10 hours at 30 ℃, finishing the reaction, and detecting the content of the D pantoic acid calcium in the obtained enzymolysis product to be 84.6 g/L.
Example 1:
(a) taking 5L of the enzymolysis product, adding 50g of active carbon, mixing well, stirring and treating at 60 ℃ for 30min, then removing thalli and active carbon by pressure filtration, collecting supernatant, and adjusting pH to 5.5 for later use.
(b) Removing macromolecular protein from the obtained clear liquid by microfiltration membrane equipment, dialyzing for 3 times in a concentrated phase, and recovering 98% of D-pantoic acid calcium and L-pantoic acid lactone; the microfiltration permeating liquid is filtered by ultrafiltration membrane equipment with molecular weight cut-off of 5000Da, concentrated phase dialysis is carried out for 4 times, and the recovery rate of D-pantoic acid calcium and L-pantoic acid lactone is 97 percent; separating the ultrafiltration permeate by a nanofiltration membrane DL1812 of general electric company, detecting the content of the concentrated-phase L-pantoic acid lactone, dialyzing for 4 times, wherein the residue ratio of the concentrated-phase L-pantoic acid lactone is less than 1 percent, the clear liquid has no D-pantoic acid calcium, and the recovery rate of the D-pantoic acid calcium and the L-pantoic acid lactone is more than 95 percent.
The obtained D-calcium pantoate-containing water solution is concentrated and crystallized to obtain a pure D-calcium pantoate product, and the purity is as follows: 99.0 percent.
Example 2:
(a) taking 5L of the enzymolysis product, adding 50g of diatomite, mixing uniformly for 30min, press-filtering to remove thallus and diatomite, collecting clear liquid, and adjusting pH to 6.0 for later use.
(b) Removing macromolecular protein from the obtained clear liquid by microfiltration membrane equipment, dialyzing for 5 times in a concentrated phase, and recovering 99% of D-pantoic acid calcium and L-pantoic acid lactone; the microfiltration permeating liquid passes through an ultrafiltration membrane with molecular weight cutoff of 3000Da, and is dialyzed for 5 times in a concentrated phase, and the recovery rate of D-pantoic acid calcium and L-pantoic acid lactone is 97 percent; separating the ultrafiltration permeate by a nanofiltration membrane DL1812 of general electric company, detecting the content of the concentrated-phase L-pantoic acid lactone, dialyzing for 7 times, wherein the residual ratio of the concentrated-phase L-pantoic acid lactone is 0.5 percent, the clear liquid has no D-pantoic acid calcium, and the recovery rate of the D-pantoic acid calcium and the L-pantoic acid lactone is more than 95 percent.
The obtained solution containing the D-calcium pantoate is concentrated and crystallized to obtain a pure D-calcium pantoate product with the purity as follows: 98.9 percent.
Example 3:
(a) taking 5L of the enzymolysis product, adding 100g of activated carbon, treating at 65 ℃ for 20min, filtering by a plate frame to remove thalli and activated carbon, collecting clear liquid, and adjusting pH to 5.6 for later use.
(b) Removing macromolecular protein from the obtained clear liquid by microfiltration membrane equipment, dialyzing for 5 times in a concentrated phase, and recovering 99% of D-pantoic acid calcium and L-pantoic acid lactone; the microfiltration permeating liquid passes through an ultrafiltration membrane with molecular weight cutoff of 3000Da, and is dialyzed for 5 times in a concentrated phase, and the recovery rate of D-pantoic acid calcium and L-pantoic acid lactone is 97 percent; separating the ultrafiltration permeate by a nanofiltration membrane PW1812 of general electric company, detecting the content of concentrated-phase L-pantoic acid lactone, dialyzing for 3 times, wherein the residual ratio of the concentrated-phase L-pantoic acid lactone is 0.5 percent, the clear liquid has no D-pantoic acid calcium, and the recovery rate of the D-pantoic acid calcium and the L-pantoic acid lactone is more than 95 percent.
The obtained D-calcium pantoate-containing water solution is concentrated and crystallized to obtain a pure D-calcium pantoate product, and the purity is as follows: 99.1 percent.
Claims (10)
1. A method for separating an acid and an ester from a mixed solution, comprising: in the first stage, adjusting the pH of the mixed solution to 5-8 by using a pH regulator, in the second stage, separating the obtained solution by using a membrane element, and respectively collecting trapped fluid and permeate; the mixed solution at least comprises acid and ester.
2. The method of separating an acid and an ester from a mixed solution according to claim 1, wherein: the pH regulator is at least one selected from magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, barium oxide, barium hydroxide, ferrous oxide, ferrous hydroxide, ferric oxide, ferric hydroxide, cupric oxide, cupric hydroxide, manganese oxide and manganese hydroxide.
3. The method of separating an acid and an ester from a mixed solution according to claim 1, wherein: the pH regulator is solid or aqueous solution.
4. The method of separating an acid and an ester from a mixed solution according to claim 1, wherein: the molecular weight cut-off of the membrane element is 200-800D.
5. The method of separating an acid and an ester from a mixed solution according to claim 1, wherein: the acid is an organic acid, and the ester is an organic acid ester.
6. The method of separating an acid and an ester from a mixed solution according to claim 5, wherein: the organic acid is connected with-COOH and-SO on the molecule3H. -RSOOH, -RCOSH, said organic acid ester being a lactide or a lactone.
7. The method of claim 5, wherein the organic acid is at least one of lactic acid, glycolic acid, L-pantoic acid, D-pantoic acid, α hydroxybutyric acid, β hydroxybutyric acid and gluconic acid, and the organic acid is at least one of glycolide, lactide, valerolactone, D-pantoic lactone, L-pantoic lactone and gluconolactone.
8. The method of separating an acid and an ester from a mixed solution according to claim 1, wherein: the concentration of acid in the mixed solution is 0.5-999g/L, and the concentration of ester is 0.5-999 g/L.
9. The method of separating an acid and an ester from a mixed solution according to claim 1, wherein: the solution further comprises a step of removing impurity components in the mixed solution before the separation by the membrane element.
10. The method of separating an acid and an ester from a mixed solution according to claim 9, wherein: the method for removing impurity components in the mixed solution comprises the following steps:
1) carrying out adsorption filtration on the mixed solution, and collecting filtrate; and/or
2) Filtering the mixed solution by adopting a membrane element with the molecular weight cutoff of 1000-10000D, and collecting the permeate; and/or
3) Treating the mixed solution by using a disk separation method, and collecting a disk separation clear solution;
the adsorption filter medium comprises activated carbon and/or diatomite; the membrane element is at least one of a microfiltration membrane, a nanofiltration membrane and an ultrafiltration membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911214041.XA CN110835185B (en) | 2019-12-02 | 2019-12-02 | Method for separating acid and ester from mixed solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911214041.XA CN110835185B (en) | 2019-12-02 | 2019-12-02 | Method for separating acid and ester from mixed solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110835185A true CN110835185A (en) | 2020-02-25 |
| CN110835185B CN110835185B (en) | 2022-11-08 |
Family
ID=69578203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911214041.XA Active CN110835185B (en) | 2019-12-02 | 2019-12-02 | Method for separating acid and ester from mixed solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110835185B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111499602A (en) * | 2020-05-14 | 2020-08-07 | 吴江 | Method for extracting D-pantolactone from D L-pantolactone split liquid by calcium salt method |
| CN112209819A (en) * | 2020-09-27 | 2021-01-12 | 安徽泰格生物科技有限公司 | Preparation method of D-pantoic acid calcium |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0320398A (en) * | 1989-06-16 | 1991-01-29 | Nippon Oil & Fats Co Ltd | Deacidifying process |
| CN101157592A (en) * | 2002-01-24 | 2008-04-09 | 巴斯福股份公司 | A process for the separation of acids from reaction mixtures by ion liquid |
| CN101547735A (en) * | 2007-03-22 | 2009-09-30 | 月岛环境工程株式会社 | Method of separating target substance according to membrane separation and apparatus therefor |
| CN101830817A (en) * | 2009-03-12 | 2010-09-15 | 刘驳谦 | Method for continuous multistage membrane separation of trimethylamine ethylene colactone from salt compound |
| CN102423646A (en) * | 2011-08-17 | 2012-04-25 | 浙江大学 | Nano-filtration membrane for separating organic compounds and salts, and preparation method thereof |
| KR20140096787A (en) * | 2013-01-29 | 2014-08-06 | 한국화학연구원 | Recovery method of highly pure organic acid and organic acid alkyl ester from organic acid fermentation solution |
| CN106277576A (en) * | 2016-08-11 | 2017-01-04 | 上海凯鑫分离技术股份有限公司 | A kind of polyester fiber alkali processes the integrated conduct method of waste water |
| CN106755143A (en) * | 2017-01-11 | 2017-05-31 | 南京工业大学 | A kind of method for extracting high-pure lactic acid continuous from lactic fermentation liquid |
-
2019
- 2019-12-02 CN CN201911214041.XA patent/CN110835185B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0320398A (en) * | 1989-06-16 | 1991-01-29 | Nippon Oil & Fats Co Ltd | Deacidifying process |
| CN101157592A (en) * | 2002-01-24 | 2008-04-09 | 巴斯福股份公司 | A process for the separation of acids from reaction mixtures by ion liquid |
| CN101547735A (en) * | 2007-03-22 | 2009-09-30 | 月岛环境工程株式会社 | Method of separating target substance according to membrane separation and apparatus therefor |
| CN101830817A (en) * | 2009-03-12 | 2010-09-15 | 刘驳谦 | Method for continuous multistage membrane separation of trimethylamine ethylene colactone from salt compound |
| CN102423646A (en) * | 2011-08-17 | 2012-04-25 | 浙江大学 | Nano-filtration membrane for separating organic compounds and salts, and preparation method thereof |
| KR20140096787A (en) * | 2013-01-29 | 2014-08-06 | 한국화학연구원 | Recovery method of highly pure organic acid and organic acid alkyl ester from organic acid fermentation solution |
| CN106277576A (en) * | 2016-08-11 | 2017-01-04 | 上海凯鑫分离技术股份有限公司 | A kind of polyester fiber alkali processes the integrated conduct method of waste water |
| CN106755143A (en) * | 2017-01-11 | 2017-05-31 | 南京工业大学 | A kind of method for extracting high-pure lactic acid continuous from lactic fermentation liquid |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111499602A (en) * | 2020-05-14 | 2020-08-07 | 吴江 | Method for extracting D-pantolactone from D L-pantolactone split liquid by calcium salt method |
| CN111499602B (en) * | 2020-05-14 | 2022-06-07 | 安徽泰格生物科技有限公司 | Method for extracting D-pantolactone from DL-pantolactone split liquid by calcium salt method |
| CN112209819A (en) * | 2020-09-27 | 2021-01-12 | 安徽泰格生物科技有限公司 | Preparation method of D-pantoic acid calcium |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110835185B (en) | 2022-11-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2220018B1 (en) | Method for purifying an alcohol from a fermentation broth | |
| CN110835185B (en) | Method for separating acid and ester from mixed solution | |
| CN101863950A (en) | Method for extracting tea saponin from oil tea cakes | |
| CN1289492C (en) | Method for extracting theaflavin | |
| CN104974032A (en) | Method of separation and extraction of D-lactic acid from sodium D-lactate fermentation liquid | |
| CN108329363B (en) | Method for removing hydroquinone in alpha-arbutin conversion solution | |
| WO2018141798A1 (en) | Process and composition | |
| CN111440167A (en) | Method for extracting pyrroloquinoline quinone from fermentation liquor | |
| JPWO2004011660A1 (en) | Method for producing ubiquinone-10-containing solution | |
| KR101540520B1 (en) | Method for succinic acid purification using reverse osmosis membrane | |
| WO2015068769A1 (en) | Method for producing purified soybean oligosaccharide solution | |
| CN101514155A (en) | Method for separating and extracting pyruvic acid from fermentation broth by an ion exchange method | |
| JP2007259821A (en) | Method for producing sugar alcohol | |
| CN211677200U (en) | System for separating acid and ester from mixed solution | |
| CN101492366A (en) | Method for extracting allomaleic acid from fermentation liquor | |
| CN104513151A (en) | Method for extracting high purity succinic acid from succinate fermentation liquid | |
| CN112774448A (en) | Method for separating acid from ester | |
| CN112774251A (en) | Method for separating acid and ester mixed solution | |
| CN111850081B (en) | Method for resolving optical isomers using supercritical fluid extraction techniques | |
| CN107245478B (en) | Extraction and purification method of pumpkin ascorbic acid oxidase | |
| CN108239056B (en) | Method for recovering mevastatin from mevastatin crystallization mother liquor | |
| CN117142683A (en) | Method for removing organic acid in amino acid fermentation liquor | |
| CN105273103A (en) | Method for preparing tea polysaccharides by combining separating membranes with chromatographic column | |
| JP4480100B2 (en) | Method for producing L-ascorbic acid-2-phosphate | |
| CN105130792A (en) | Method for separating and purifying (R)-(-)-mandelic acid synthesized with biological method |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |