CN105837431A - Method for separating sodium acetate from mixed system of sodium acetate and sodium sulfate - Google Patents
Method for separating sodium acetate from mixed system of sodium acetate and sodium sulfate Download PDFInfo
- Publication number
- CN105837431A CN105837431A CN201610203630.8A CN201610203630A CN105837431A CN 105837431 A CN105837431 A CN 105837431A CN 201610203630 A CN201610203630 A CN 201610203630A CN 105837431 A CN105837431 A CN 105837431A
- Authority
- CN
- China
- Prior art keywords
- sodium
- sodium acetate
- sodium sulfate
- sulfate
- acetate
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/16—Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for separating sodium acetate from a mixed system of sodium acetate and sodium sulfate, belonging to the field of separation and recovery of sodium acetate. According to the separation method, calcium acetate is added into a mixed solution to form calcium sulfate precipitate and then water is properly removed so as to allow sodium sulfate to be precipitated, so desulphurization and crystallization of the mixed solution is realized and sodium acetate is obtained. The method comprises the following steps: preparation of the mixed solution; preparation of calcium acetate; precipitation and desulphurization; and crystallization of sodium acetate. The method for separating sodium acetate from the mixed system of sodium acetate and sodium sulfate is simple in composition of a precipitating agent and low in preparation cost; a part of sulfate ions in the mixed solution are precipitated in the form of sodium sulfate, and rest sulfate ions is crystallized and precipitated in the form of sodium sulfate after proper dehydration, so good desulphurization effect is obtained, and the sodium acetate can be recovered through crystallization and can be recycled and used in industrial production; and the method is good in operability, low in cost, small in energy consumption and applicable to industrial production and waste liquid treatment of related fields.
Description
Technical field
The present invention relates to sodium acetate separation and recovery field, particularly relate to a kind of sodium sulfate and sodium acetate
The method that sodium acetate in mixed system separates.
Background technology
Sodium acetate molecular formula is CH3COONa or NaAc, also referred to as anhydrous sodium acetate, in work
Industry can be used as the stabilizer of the metallic elements such as lead, zinc, aluminum, ferrum, cobalt, nickel in producing, organic
The esterifying agent of synthesis, it is possible to as buffer agent, pH adjusting agent, Chemical Manufacture and some
Applications in Food Industry is extensive, the most often produces a large amount of industrial wastes containing sodium acetate.?
In some processing procedures, waste liquid exists sulfate ion, this kind of waste liquid containing sodium acetate simultaneously
Can be processed by desulfurization, crystallize the recycling realizing sodium acetate.Currently with precipitating ion
The solidification removing realizing sulfate radical is a kind of commonplace way, the precipitant probed into out
There are barium chloride, nitric hydrate aluminum and calcium hydroxide and some compounding ingredients precipitant, and uncomfortable
Desulfurization for the industrial wastes containing a large amount of sodium acetates processes.It is simple in order to explore a kind of composition,
Low cost, desulfurized effect is good, be applicable to sodium acetate and the desulfurization precipitant of sodium sulfate mixed system,
We have probed into and have utilized calcium ion to realize sodium sulfate and vinegar as precipitating ion by the appropriate water that removes
The desulfurization of acid sodium mixed solution, and crystallize the method obtaining the higher sodium acetate of purity, obtain
Preferably effect.
Summary of the invention
The present invention solves sodium acetate and sodium sulfate mixed solution desulfurized effect is poor, and efficiency is low, heavy
Shallow lake agent complicated components, the technical problem that cost is high, therefore provide a kind of sodium acetate and sodium sulfate to mix
Close the method separating sodium acetate in solution, utilize calcium ion to pass through evaporation water loss as precipitating ion
Calcium sulfate and sodium sulfate Precipitation is made to realize sodium acetate and the desulfurization of sodium sulfate system and acetic acid
The recovery of sodium, method is simple, low cost, and desulfurized effect is good, and the sodium acetate response rate is high.
To achieve the above object, the technical scheme is that a kind of sodium acetate and sulphuric acid
The method separating sodium acetate in sodium mixed system, it is characterised in that add vinegar in mixed solution
Acid calcium forms calcium sulfate precipitation, appropriate except separating out sodium sulfate after water, it is achieved the desulfurization of mixed solution,
Crystallization obtains sodium acetate, specifically includes following steps:
(1) mixed solution prepares: take the mixed solution of sodium sulfate and sodium acetate, wherein solution
Sulfur acid na concn is 0.18~0.34mol/L, and sodium acetate concentration is 3.65~4.95mol/L;
(2) prepared by calcium acetate: by calcium oxide and water mix and blend, obtain paste liquid or solid-liquid
The mixed system coexisted, adds acetic acid under stirring, react to solution clarification, standby;
(3) precipitation desulfurization: step (2) gained solution is added step (1) gained acetic acid
In sodium and sodium sulfate mixed system, carrying out heated and stirred simultaneously and make solution mix homogeneously, system becomes
Muddiness, i.e. has calcium sulfate precipitation to produce, and continuous heating stirring makes mixed solution dehydration, along with water
The evaporation divided, precipitation increases, and solid sodium sulfate separates out in the lump, and insulation is filtered to remove sulfur acid calcium
With the precipitation of sodium sulfate, sulfate radical clearance is 90.0%~95.0%;
(4) sodium acetate crystallization: step (3) gained filtrate is transferred in the container of cleaning,
Room temperature stands, and keeps 2~6 hours, make acetic acid after being cooled to 10~20 DEG C under this temperature range
Sodium perfect crystalline, after having crystallized, room temperature filters, and obtains with adsorbing water and knot containing of impurity
The sodium acetate crystal of brilliant water, except after water, the response rate of sodium acetate is 60~95%, purity is
85.0~95.0%.
In described step (1), sodium sulfate concentration is 0.23mol/L, 0.26mol/L, 0.28mol/L
In one, the concentration of sodium acetate is in 4.40mol/L, 4.70mol/L, 4.80mol/L
Kind.
Calcium Oxide Dosage and the mol ratio of sodium sulfate in former mixed solution in described step (2)
For (2~3): 1, adding the amount of water with the mass ratio of calcium oxide be (6~8): 1, addition acetic acid
Amount is (1.7~3.0) with the mol ratio of calcium oxide: 1, and mixing speed is 50~300rpm.
The appropriate removal process of evaporation water loss process ie in solution system in described step (3),
Dehydration percentage ratio is 28%~42%, and its dehydration percentage ratio is that evaporation water loss quality accounts for total solution and contains
The percentage ratio of water quality, the non-percentage ratio accounting for solution gross mass, the heating-up temperature of step (3)
Being all 60~100 DEG C, mixing speed is all 50~300rpm, and insulation filtration temperature is 50~100 DEG C,
Insulation is filtered into insulation decompression sucking filtration or insulation filter pressing, and insulation decompression sucking filtration selects buchner funnel behaviour
Making, pressure filter operation is selected in insulation filter pressing.
In described step (4), room temperature is filtered into room temperature decompression sucking filtration or room temperature filter pressing, room temperature
Decompression sucking filtration selects buchner funnel operation, and pressure filter operation is selected in room temperature filter pressing.
Having the beneficial effect that of the technique scheme of the present invention:
(1) present invention is by adding calcium acetate and carrying out, in right amount except water, making in mixed solution
Sulfate ion is with the form Precipitation of calcium sulfate and sodium sulfate, it is achieved the desulfurization of mixed solution,
The most crystallized sodium acetate that obtains, calcium acetate is reacted by acetic acid and calcium oxide and obtains, and production cost is low
Honest and clean, reduce processing cost, precipitant component is simple, and desulfurized effect is good.
(2) steam being evaporated in the present invention can carry out condensation recovery by chiller,
Recirculation is in other steps, it is achieved recycling of resource, reduces the cost of water for industrial use.
(3) crystallizing sodium acetate content in the impure sodium acetate crystal obtained in the present invention is
85.0~95.0%, meet the purity requirement in commercial production, in can being directly recycled for producing,
Reduce production cost.
(4) present invention process flow process is simple, has operability, uses simple technique to set
Standby can process, with low cost, and recycling of water and sodium acetate can be realized, save
Energy consumption.
Accompanying drawing explanation
Sodium acetate that Fig. 1 provides for the present invention and sodium sulfate mixed system separate sodium acetate
The schematic diagram of method.
Detailed description of the invention
For making the technical problem to be solved in the present invention, technical scheme and advantage clearer, below
To be described in detail in conjunction with specific embodiments.
A kind of method separating sodium acetate in sodium acetate and sodium sulfate mixed system, specific embodiment
As follows:
Embodiment 1
(1) take 74mL sodium sulfate and sodium acetate mixed solution is standby, wherein sodium sulfate concentration
For 0.19mol/L, sodium acetate concentration is 3.65mol/L.(2) 1.60g calcium oxide and 10mL are weighed
Water mixes, and the lower 2.80mL acetic acid reaction that adds of stirring is to solution clarification.(3) by step (2)
Gained solution adds in the solution of step (1), 100 DEG C of heated and stirred, and evaporation removes 21g water,
I.e. dehydration percentage ratio is 29%.80 DEG C of insulation sucking filtration, obtain the filter cake of sulfur acid calcium and sodium sulfate.
(4) filtrate that sucking filtration obtains being quickly transferred in open-top receptacle, left at room temperature is cooled to
Keep 3 hours after 10 DEG C, room temperature sucking filtration, obtain transparent sodium acetate crystal.The sodium acetate response rate
Being 60%, sulfate radical clearance is 90.2%.
Embodiment 2
(1) take 82mL sodium sulfate and sodium acetate mixed solution is standby, wherein sodium sulfate concentration
For 0.26mol/L, sodium acetate concentration is 4.70mol/L.(2) 3.00g calcium oxide and 21mL are weighed
Water mixes, and the lower 9.20mL acetic acid reaction that adds of stirring is to solution clarification.(3) by step (2)
Gained solution adds in the solution of step (1), 60 DEG C of heated and stirred, and evaporation removes 34g water,
I.e. dehydration percentage ratio is 40%.50 DEG C of insulation sucking filtration, obtain the filter cake of sulfur acid calcium and sodium sulfate.
(4) filtrate that sucking filtration obtains being quickly transferred in open-top receptacle, left at room temperature is cooled to
Keep 5 hours after 15 DEG C, room temperature sucking filtration, obtain transparent sodium acetate crystal.The sodium acetate response rate
Being 95%, sulfate radical clearance is 93.1%.
Embodiment 3
(1) take 82mL sodium sulfate and sodium acetate mixed solution is standby, wherein sodium sulfate concentration
For 0.34mol/L, sodium acetate concentration is 4.95mol/L.(2) 3.19g calcium oxide and 20mL are weighed
Water mixes, and the lower 7.60mL acetic acid reaction that adds of stirring is to solution clarification.(3) by step (2)
Gained solution adds in the solution of step (1), 85 DEG C of heated and stirred, and evaporation removes 29g water,
I.e. dehydration percentage ratio is 34%.95 DEG C of insulation sucking filtration, obtain the filter cake of sulfur acid calcium and sodium sulfate.
(4) filtrate that sucking filtration obtains being quickly transferred in open-top receptacle, left at room temperature is cooled to
Keep 2 hours after 20 DEG C, room temperature sucking filtration, obtain transparent sodium acetate crystal.The sodium acetate response rate
Being 73%, sulfate radical clearance is 94.7%.
Embodiment 4
(1) take 82mL sodium sulfate and sodium acetate mixed solution is standby, wherein sodium sulfate concentration
For 0.23mol/L, sodium acetate concentration is 4.40mol/L.(2) 2.85g calcium oxide and 22mL are weighed
Water mixes, and the lower 7.90mL acetic acid reaction that adds of stirring is to solution clarification.(3) by step (2)
Gained solution adds in the solution of step (1), 90 DEG C of heated and stirred, and evaporation removes 30g water,
I.e. dehydration percentage ratio is 32%.60 DEG C of insulation sucking filtration, obtain the filter cake of sulfur acid calcium and sodium sulfate.
(4) filtrate that sucking filtration obtains being quickly transferred in open-top receptacle, left at room temperature is cooled to
Keep 6 hours after 15 DEG C, room temperature sucking filtration, obtain transparent sodium acetate crystal.The sodium acetate response rate
Being 84%, sulfate radical clearance is 91.6%.
Embodiment 5
(1) take 82mL sodium sulfate and sodium acetate mixed solution is standby, wherein sodium sulfate concentration
For 0.28mol/L, sodium acetate concentration is 4.80mol/L.(2) 3.86g calcium oxide and 30mL are weighed
Water mixes, and the lower 7.92mL acetic acid reaction that adds of stirring is to solution clarification.(3) by step (2)
Gained solution adds in the solution of step (1), 80 DEG C of heated and stirred, and evaporation removes 36g water,
I.e. dehydration percentage ratio is 35%.75 DEG C of insulation sucking filtration, obtain the filter cake of sulfur acid calcium and sodium sulfate.
(4) filtrate that sucking filtration obtains being quickly transferred in open-top receptacle, left at room temperature is cooled to
Keep 4 hours after 18 DEG C, room temperature sucking filtration, obtain transparent sodium acetate crystal.The sodium acetate response rate
Being 87%, sulfate radical clearance is 92.2%.
The above is the preferred embodiment of the present invention, it is noted that for the art
Those of ordinary skill for, on the premise of without departing from principle of the present invention, it is also possible to do
Going out some improvements and modifications, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (5)
1. the method separating sodium acetate in sodium acetate and sodium sulfate mixed system, its feature exists
In, mixed solution adds calcium acetate and forms calcium sulfate precipitation, appropriate except separating out sulphuric acid after water
Sodium, it is achieved the desulfurization of mixed solution, crystallization obtains sodium acetate, specifically includes following steps:
(1) mixed solution prepares: take the mixed solution of sodium sulfate and sodium acetate, wherein solution
Sulfur acid na concn is 0.18~0.34mol/L, and sodium acetate concentration is 3.65~4.95mol/L;
(2) prepared by calcium acetate: by calcium oxide and water mix and blend, obtain paste liquid or solid-liquid
The mixed system coexisted, adds acetic acid under stirring, react to solution clarification, standby;
(3) precipitation desulfurization: step (2) gained solution is added step (1) gained acetic acid
In sodium and sodium sulfate mixed system, carrying out heated and stirred simultaneously and make solution mix homogeneously, system becomes
Muddiness, i.e. has calcium sulfate precipitation to produce, and continuous heating stirring makes mixed solution dehydration, along with water
The evaporation divided, precipitation increases, and solid sodium sulfate separates out in the lump, and insulation is filtered to remove sulfur acid calcium
With the precipitation of sodium sulfate, sulfate radical clearance is 90.0%~95.0%;
(4) sodium acetate crystallization: step (3) gained filtrate is transferred in the container of cleaning,
Room temperature stands, and keeps 2~6 hours, make acetic acid after being cooled to 10~20 DEG C under this temperature range
Sodium perfect crystalline, after having crystallized, room temperature filters, and obtains containing absorption water and the acetic acid of water of crystallization
Sodium crystal, except after water, the response rate of sodium acetate is 60~95%, purity is 85.0~95.0%.
Sodium acetate the most according to claim 1 and sodium sulfate mixed system separate acetic acid
The method of sodium, it is characterised in that in described step (1), sodium sulfate concentration be 0.23mol/L,
One in 0.26mol/L, 0.28mol/L, the concentration of sodium acetate is 4.40mol/L, 4.70mol/L,
One in 4.80mol/L.
Sodium acetate the most according to claim 1 and sodium sulfate mixed system separate acetic acid
The method of sodium, it is characterised in that in described step (2) Calcium Oxide Dosage with former mix molten
In liquid, the mol ratio of sodium sulfate is (2~3): 1, and the mass ratio of the amount and calcium oxide that add water is
(6~8): 1, the mol ratio adding acetic acid amount and calcium oxide is (1.7~3.0): 1, stirring speed
Degree is 50~300rpm.
Sodium acetate the most according to claim 1 and sodium sulfate mixed system separate acetic acid
The method of sodium, it is characterised in that the instant liquid of evaporation water loss process in described step (3)
The appropriate removal process of system, its dehydration percentage ratio is that evaporation water loss quality accounts for total solution containing water quality
Percentage ratio, the non-percentage ratio accounting for solution gross mass, dehydration percentage ratio is 28%~42%, step
Suddenly the heating-up temperature of (3) is 60~100 DEG C, and mixing speed is 50~300rpm, insulation
Filtration temperature is 50~100 DEG C, and insulation is filtered into insulation decompression sucking filtration or insulation filter pressing, insulation
Decompression sucking filtration selects buchner funnel operation, insulation filter pressing to select pressure filter operation.
Sodium acetate the most according to claim 1 and sodium sulfate mixed system separate acetic acid
The method of sodium, it is characterised in that in described step (4) room temperature be filtered into room temperature decompression take out
Filter or room temperature filter pressing, room temperature decompression sucking filtration selects buchner funnel operation, room temperature filter pressing selection filter pressing
Machine operates.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610203630.8A CN105837431B (en) | 2016-04-01 | 2016-04-01 | A kind of method that sodium acetate is detached in sodium acetate and sodium sulphate mixed system |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610203630.8A CN105837431B (en) | 2016-04-01 | 2016-04-01 | A kind of method that sodium acetate is detached in sodium acetate and sodium sulphate mixed system |
Publications (2)
Publication Number | Publication Date |
---|---|
CN105837431A true CN105837431A (en) | 2016-08-10 |
CN105837431B CN105837431B (en) | 2018-11-06 |
Family
ID=56596948
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610203630.8A Expired - Fee Related CN105837431B (en) | 2016-04-01 | 2016-04-01 | A kind of method that sodium acetate is detached in sodium acetate and sodium sulphate mixed system |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105837431B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110627093A (en) * | 2019-09-02 | 2019-12-31 | 南京格洛特环境工程股份有限公司 | Recycling treatment process of sodium acetate waste salt in glufosinate-ammonium production |
CN113292416A (en) * | 2021-06-04 | 2021-08-24 | 枣庄市泰瑞精细化工有限公司 | Production method for preparing sodium acetate by utilizing dihydroxy naphthalene waste liquid |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010129637A1 (en) * | 2009-05-05 | 2010-11-11 | American Process, Inc. | A system and process for separating pure chemicals from biomass extract |
CN104086398A (en) * | 2014-07-15 | 2014-10-08 | 中南大学 | Method for separating and recovering oxalic acid from waste oxalic acid liquor |
-
2016
- 2016-04-01 CN CN201610203630.8A patent/CN105837431B/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010129637A1 (en) * | 2009-05-05 | 2010-11-11 | American Process, Inc. | A system and process for separating pure chemicals from biomass extract |
CN104086398A (en) * | 2014-07-15 | 2014-10-08 | 中南大学 | Method for separating and recovering oxalic acid from waste oxalic acid liquor |
Non-Patent Citations (3)
Title |
---|
吴家全等: "氯碱工艺中脱除硫酸根方法的研究", 《氯碱工业》 * |
张乃慧: "脱除浓NaCl水溶液中硫酸钠的工艺", 《中国氯碱》 * |
陈笃生: "酷酸钠同时脱硫脱硝法", 《中氮肥》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110627093A (en) * | 2019-09-02 | 2019-12-31 | 南京格洛特环境工程股份有限公司 | Recycling treatment process of sodium acetate waste salt in glufosinate-ammonium production |
CN113292416A (en) * | 2021-06-04 | 2021-08-24 | 枣庄市泰瑞精细化工有限公司 | Production method for preparing sodium acetate by utilizing dihydroxy naphthalene waste liquid |
Also Published As
Publication number | Publication date |
---|---|
CN105837431B (en) | 2018-11-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103145187B (en) | Production technology of harmless high-purity vanadium pentoxide | |
CN103402917A (en) | Method and device for recovering boric acid | |
CN104003445A (en) | Method for producing high-solubility ammonium heptamolybdate | |
CN102491377B (en) | A kind of method of lithium hydroxide purifying | |
CN103936034B (en) | Preparation method of high-purity sodium iodide powder | |
CN105366722A (en) | Normal temperature extraction method for producing high-purity vanadium pentoxide | |
CN105837431A (en) | Method for separating sodium acetate from mixed system of sodium acetate and sodium sulfate | |
CN202688007U (en) | High-purity ammonium paratungstate preparation system | |
CN114574699B (en) | Method for preparing ammonium metavanadate and ammonium molybdate from vanadium-molybdenum-containing solution | |
CN104773749A (en) | Method for preparing high-purity calcium fluoride in ethanol system | |
CN110204437A (en) | A method of producing L MALIC ACID coproduction succinic acid | |
CN101838750A (en) | Method for performing direct acid adjusting closed cycle on ammonium paratungstate crystallization mother liquor | |
CN1736870A (en) | Method for preparing potassium nitrate using nitric acid conversion methdo | |
CN103012114A (en) | Method of synchronously preparing DL-tartaric acid and DL-potassium hydrogen tartrate | |
CN1063730C (en) | Technology for producing magnesium sulfate in treatment of titanium white waste sulfuric acid | |
CN102126756A (en) | Method for producing industrial grade ammonium paramolybdate | |
CN102417207B (en) | Process for preparing ammonium dimolybdate crystal by using sulfuric acid and molybdenum calcine | |
CN101182036A (en) | Technique for preparing high-purity vanadium pentoxide by high-vanadium edulcoration | |
CN114573006B (en) | Method for purifying and recovering lithium by-product lithium-containing crude sodium sulfate in lithium extraction process of nickel cobalt lithium manganate anode material recovery | |
CN105566098A (en) | Method for combined production of high purity crystalline calcium acetate and waterless calcium acetate | |
CN105669511B (en) | A kind of hydroxyproline refining methd | |
CN109485558A (en) | A kind of method of purification of long-chain biatomic acid | |
CN105601499B (en) | A kind of separation method of the sodium acetate solution of sulfur acid sodium | |
CN114956128A (en) | Method and system for preparing battery-grade lithium hydroxide and lithium carbonate | |
CN101928039A (en) | Method for preparing ammonium metatungstate |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20181106 |
|
CF01 | Termination of patent right due to non-payment of annual fee |