CN108911950B - Equipment and method for separating alcohol and ammonium carbonate in wastewater - Google Patents
Equipment and method for separating alcohol and ammonium carbonate in wastewater Download PDFInfo
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- CN108911950B CN108911950B CN201810653515.XA CN201810653515A CN108911950B CN 108911950 B CN108911950 B CN 108911950B CN 201810653515 A CN201810653515 A CN 201810653515A CN 108911950 B CN108911950 B CN 108911950B
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/42—Regulation; Control
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/26—Carbonates or bicarbonates of ammonium
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Abstract
The invention discloses equipment and a method for separating alcohol and ammonium carbonate in wastewater, wherein the equipment comprises a first-stage rectifying tower, a second-stage rectifying tower, a third-stage rectifying tower, an ammonium carbonate crystallizing kettle and an alcohol neutralizing tank, alcohol is evaporated out, condensed and separated by controlling rectifying conditions, and ammonium carbonate gas phase and alcohol are separated and then condensed, crystallized and recovered. The method realizes effective separation of alcohol and ammonium carbonate in the wastewater, and can be used for industrial production.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to equipment and a method for separating alcohol and ammonium carbonate in wastewater.
Background
The glufosinate-ammonium is an efficient and low-toxic organic phosphorus herbicide and has wide market prospect. Patents CN102372739 and CN105037060 disclose a process for producing glufosinate-ammonium by hydrolyzing hydroxy nitrile or hydantoin compounds with ammonium carbonate, in which water distilled from hydrolysate and ammonium carbonate are mechanically used for hydrolysis reaction, thereby realizing zero discharge of waste water and waste salt. However, the actual condition is that by-products of methanol and ethanol are produced by hydrolysis, and the content of methanol and ethanol in a hydrolysis system is increased by applying a hydrolysis solvent, so that the pressure of the reaction system is increased. Therefore, the removal of methanol and ethanol from the mixture for reuse is a problem to be solved.
The method for removing a large amount of alcohol in water is mainly realized by rectification. However, because the decomposition temperature of ammonium carbonate is close to the rectification temperature of methanol and ethanol, ammonium carbonate is evaporated out along with alcohol in the rectification process, and pipeline blockage is caused by pipeline crystallization, so that the separation of alcohol in the mixture is difficult to realize. At present, the research on the separation of the aqueous solution containing ammonium carbonate and alcohol is less, and no relevant literature report exists, and no relevant process for industrially separating and recovering the aqueous solution containing ammonium carbonate and alcohol exists.
Disclosure of Invention
Aiming at the technical current situation, the invention provides an industrialized device capable of efficiently separating alcohol and ammonium carbonate from wastewater in a glufosinate-ammonium production process, and provides a separation method using the device.
In order to achieve the purpose, the invention adopts the following technical scheme:
an apparatus for separating alcohol and ammonium carbonate in wastewater comprises a first-stage rectifying tower, a second-stage rectifying tower, a third-stage rectifying tower, an ammonium carbonate crystallizing kettle and an alcohol neutralizing tank;
the top of the first-stage rectifying tower is connected with a first-stage condenser, a liquid discharge port of the condenser is respectively connected with the top of the first-stage rectifying tower and a feed port of the second-stage rectifying tower, and a gas outlet is connected with a feed port of an ammonium carbonate crystallization kettle;
the top of the second-stage rectifying tower is connected with a second-stage condenser, a liquid discharge port of the condenser is respectively connected with the top of the second-stage rectifying tower and a feed inlet of an alcohol neutralization tank, and a gas outlet is connected with a feed inlet of an ammonium carbonate crystallization kettle;
the alcohol neutralization tank is connected with an acid metering tank, and a discharge port of the alcohol neutralization tank is connected with a feed port of the third-stage rectifying tower;
the top of the third-stage rectifying tower is connected with a third-stage condenser, the discharge part of the condenser reflows to the third-stage rectifying tower, and the rest enters an alcohol finished product tank;
and the first-stage condenser and the second-stage condenser are respectively provided with a heat preservation device respectively on a connecting pipeline at the top of the corresponding rectifying tower and a connecting pipeline between the first-stage condenser and the second-stage condenser and the ammonium carbonate crystallization kettle respectively.
Further, a liquid discharge port of the first-stage condenser is also connected with a feed inlet of the ammonium carbonate crystallization kettle.
Further, a liquid discharge port of the primary condenser is connected with a primary alcohol receiving tank firstly, and the liquid is discharged from a discharge port of the primary alcohol receiving tank; and/or:
the liquid discharge port of the secondary condenser is connected with the secondary alcohol receiving tank firstly, and the secondary alcohol is discharged from the discharge port of the secondary alcohol receiving tank.
Further, a discharge hole of the ammonium carbonate crystallization kettle is connected with solid-liquid separation equipment, and the top of the ammonium carbonate crystallization kettle is connected with a tail gas absorption tank.
Furthermore, a liquid outlet of the solid-liquid separation equipment is connected with a feed inlet of the secondary rectifying tower.
Further, a liquid outlet of the solid-liquid separation equipment is connected with the secondary rectifying tower through an alcohol storage tank.
Further, the liquid outlet of the primary condenser is also connected with the secondary rectifying tower through an alcohol storage tank.
Further, the first-stage rectifying tower, the second-stage rectifying tower and the third-stage rectifying tower are packed towers, plate towers or combined towers consisting of the packed towers and the plate towers, wherein the plate towers are sieve plate towers, perforated plate towers, plate float valve towers or plate bubble-cap towers; the number of theoretical plates of stripping sections of the first-stage rectifying tower and the second-stage rectifying tower is 5-10, the number of theoretical plates of the rectifying sections is 20-30, and the number of theoretical plates of the rectifying sections of the third-stage rectifying tower is 20-30.
The invention also provides a method for separating alcohol and ammonium carbonate in wastewater by using the equipment, which comprises the following steps:
continuously pumping wastewater containing alcohol and ammonium carbonate into a first-stage rectifying tower, heating and rectifying, introducing 40-50 ℃ hot water into a first-stage condenser (11) and a second-stage condenser (21), and keeping the temperature of 50-60 ℃ by a heat preservation device through the first-stage condenser and the second-stage condenser and connecting pipelines at the top of the corresponding rectifying tower and between the first-stage condenser and the second-stage condenser and connecting pipelines of the first-stage condenser and the second-stage condenser and an ammonium carbonate crystallization kettle respectively; the residual gas phase after condensation of the first-stage condenser enters an ammonium carbonate crystallization kettle to crystallize and generate ammonium carbonate solid, the condensed first-stage rectification alcohol enters a second-stage rectification tower to be rectified, the residual gas phase after condensation of the tower top enters the ammonium carbonate crystallization kettle to crystallize and generate ammonium carbonate solid, the condensed second-stage rectification alcohol enters an alcohol neutralization tank, the condensed second-stage rectification alcohol enters a third-stage rectification tower to be rectified after being neutralized to be neutral by acid, and the third-stage condenser discharges to an alcohol finished product tank; the tower bottoms of the first-stage rectifying tower and the second-stage rectifying tower are discharged to be qualified water, and the tower bottom of the third-stage rectifying tower is discharged to be a small amount of ammonium sulfate solution.
Further, the tower top temperature of the first-stage rectifying tower, the second-stage rectifying tower and the third-stage rectifying tower is 64-80 ℃; the temperature of the tower kettle is 80-105 ℃, the pressure in the rectifying tower is 0.1 KPa-1.1 KPa, and the reflux ratio at the top of the tower is 2: 1-10: 1; and/or:
the temperature in the ammonium carbonate crystallization kettle is 0-20 ℃, and the crystallization solvent is methanol or ethanol; and/or:
the acid used for neutralization in the alcohol neutralization tank is any one of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid and acetic acid.
Compared with the prior art, the method has the advantages that the alcohol and the ammonium carbonate in the wastewater are effectively separated, the temperature of the condenser is controlled, the ammonium carbonate is kept gasified and enters the crystallization kettle for crystallization while the alcohol is condensed, the alcohol is mainly condensed and recovered in the condenser, and the main problem of equipment blockage in the rectification of the mixture containing the alcohol and the ammonium carbonate is solved. Ammonium carbonate has certain solubility in water-containing alcohol, the ammonium carbonate content in alcohol is higher in the alcohol by primary rectification, separation of water, alcohol and ammonium carbonate is realized by secondary rectification, and a small amount of ammonia in alcohol is removed by rectification after neutralization, so that the alcohol meets higher quality requirements.
The ammonium carbonate is insoluble in alcohol, alcohol can be used as a crystallization solvent during crystallization, the primary rectification alcohol part is used as the crystallization solvent of the ammonium carbonate, the cost is further reduced, after crystallization, solid-liquid separation equipment such as a centrifuge is used for separation, solid ammonium carbonate is recovered, and liquid alcohol continues to enter subsequent processes such as secondary rectification.
Drawings
FIG. 1 is a schematic diagram of an apparatus for separating alcohol and ammonium carbonate from wastewater according to the present invention.
In the drawings: the system comprises a first-stage rectifying tower 1, a first-stage condenser 11, a first-stage alcohol receiving tank 12, a second-stage rectifying tower 2, a second-stage condenser 21, a second-stage alcohol receiving tank 22, a third-stage rectifying tower 3, a third-stage condenser 31, an alcohol finished product tank 32, an ammonium carbonate crystallization kettle 4, solid-liquid separation equipment 41, an alcohol storage tank 42, a tail gas absorption tank 43, an alcohol neutralization tank 5 and an acid metering tank 51.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The equipment for separating alcohol and ammonium carbonate in wastewater comprises a primary rectifying tower 1, a secondary rectifying tower 2, a tertiary rectifying tower 3, an ammonium carbonate crystallization kettle 4 and an alcohol neutralization tank 5;
the top of the first-stage rectifying tower 1 is connected with a first-stage condenser 11, a liquid discharge port of the condenser is respectively connected with the top of the first-stage rectifying tower 1 and a feed port of the second-stage rectifying tower 2, and a gas outlet is connected with a feed port of an ammonium carbonate crystallization kettle 4;
the top of the secondary rectifying tower 2 is connected with a secondary condenser 21, a liquid discharge port of the condenser is respectively connected with the top of the secondary rectifying tower 2 and a feed port of the alcohol neutralization tank 5, and a gas outlet is connected with a feed port of the ammonium carbonate crystallization kettle 4;
an acid metering tank 51 is connected to the alcohol neutralization tank 5, and a discharge port of the alcohol neutralization tank 5 is connected with a feed port of the third-stage rectifying tower 3;
the top of the third-stage rectifying tower 3 is connected with a third-stage condenser 31, part of the discharged material of the condenser reflows to the third-stage rectifying tower 3, and the rest enters an alcohol finished product tank 32;
and the first-stage condenser and the second-stage condenser are respectively provided with a heat preservation device 8 with a connecting pipeline at the top of the corresponding rectifying tower and a connecting pipeline with the ammonium carbonate crystallization kettle.
The liquid discharge port of the first-stage condenser 11 in this embodiment is also connected with the feed inlet of the ammonium carbonate crystallization kettle 4.
The liquid discharge port of the primary condenser 11 is firstly connected with the primary alcohol receiving tank 12 and is discharged from the discharge port of the primary alcohol receiving tank 12;
the liquid discharge port of the secondary condenser 21 is connected with the secondary alcohol receiving tank 22, and the liquid is discharged from the discharge port of the secondary alcohol receiving tank 22.
The discharge hole of the ammonium carbonate crystallization kettle 4 is connected with a solid-liquid separation device 41, and the top of the ammonium carbonate crystallization kettle 4 is connected with a tail gas absorption tank 43.
The liquid outlet of the solid-liquid separation device 41 is connected with the secondary rectifying tower 2 through an alcohol storage tank 42.
The liquid outlet of the primary condenser 11 is also connected to the secondary rectification column 2 via an alcohol storage tank 42.
The first-stage rectifying tower 1, the second-stage rectifying tower 2 and the third-stage rectifying tower 3 are packed towers, plate towers or combined towers consisting of the packed towers and the plate towers, wherein the plate towers are sieve plate towers, perforated plate towers, floating valve towers, plate floating valve towers, bubble cap towers or plate bubble cap towers; the number of the theoretical plate numbers of the stripping sections of the first-stage rectifying tower 1 and the second-stage rectifying tower 2 is 5-10, the number of the theoretical plate numbers of the rectifying sections is 20-30, and the number of the theoretical plate numbers of the rectifying sections in the third-stage rectifying tower 3 is 20-30.
The method for separating alcohol and ammonium carbonate in wastewater by using the equipment comprises the following steps:
continuously pumping wastewater containing alcohol and ammonium carbonate into a first-stage rectifying tower 1, heating and rectifying, introducing 40-50 ℃ hot water into a first-stage condenser (11) and a second-stage condenser (21), keeping the temperature of 50-60 ℃ by a heat preservation device 8 through the first-stage condenser 11 and the second-stage condenser 21 and connecting pipelines at the top of the corresponding rectifying tower and connecting pipelines between the first-stage condenser 11 and the second-stage condenser 21 and an ammonium carbonate crystallization kettle 4, and introducing 40-50 ℃ hot water into the first-stage condenser 11 and the second-stage condenser 21; the residual gas phase after condensation of the first-stage condenser 11 enters an ammonium carbonate crystallization kettle 4 to crystallize to generate ammonium carbonate solid, the condensed first-stage rectification alcohol enters a second-stage rectification tower 2 to be rectified, the residual gas phase after condensation at the tower top enters the ammonium carbonate crystallization kettle 4 to crystallize to generate the ammonium carbonate solid, the temperature in the ammonium carbonate crystallization kettle 4 is 0-20 ℃, a crystallization solvent methanol or ethanol exists in the crystallization kettle, the first-stage rectification alcohol can be used as the crystallization solvent, the ammonium carbonate solid is separated and recovered through solid-liquid separation equipment 41 such as a centrifugal machine after crystallization, and the alcohol solvent enters the second-stage rectification tower to be continuously rectified; the condensed secondary rectification alcohol enters an alcohol neutralization tank 5, is neutralized to be neutral by acid (sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid or acetic acid) and then enters a tertiary rectification tower 3 for rectification, and the tertiary condenser 31 discharges to an alcohol finished product tank 32; the bottom of the first-stage rectifying tower 1 and the second-stage rectifying tower 2 is discharged to be qualified water, and the bottom of the third-stage rectifying tower 3 is discharged to be a small amount of ammonium sulfate solution.
The tower top temperature of the first-stage rectifying tower 1, the second-stage rectifying tower 2 and the third-stage rectifying tower 3 is 64-80 ℃; the temperature of the tower kettle is 80-105 ℃, the pressure in the rectifying tower is 0.1 KPa-1.1 KPa, and the reflux ratio at the top of the tower is 2: 1-10: 1.
The separation effect of the present invention will be described below by way of a specific separation example.
Examples 1 to 3: the first-stage rectifying tower 1 and the second-stage rectifying tower 2 are packed towers, the number of theoretical plates of a stripping section is 8, the number of theoretical plates of a rectifying section is 25, the reflux ratio is 5:1, the third-stage rectifying tower is a packed tower, the number of theoretical plates is 25, and the reflux ratio is 3: 1; the pressure in each rectifying tower is 0.1 KPa.
Example 4: the first-stage rectifying tower 1 and the second-stage rectifying tower 2 are sieve plate towers, the number of theoretical plates of a stripping section is 5, the number of theoretical plates of a rectifying section is 20, the reflux ratio is 8:1, the third-stage rectifying tower is a sieve plate tower, the number of theoretical plates is 20, and the reflux ratio is 5: 1; the pressure in each rectifying tower is 1.1 KPa.
Other conditions and separation effects of the examples are shown in table 1.
TABLE 1 operating conditions and separation Effect of examples 1-4
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. An equipment of alcohol and ammonium carbonate in separation waste water which characterized in that: comprises a first-stage rectifying tower (1), a second-stage rectifying tower (2), a third-stage rectifying tower (3), an ammonium carbonate crystallization kettle (4) and an alcohol neutralization tank (5);
the top of the first-stage rectifying tower (1) is connected with a first-stage condenser (11), a liquid discharge port of the condenser is respectively connected with the top of the first-stage rectifying tower (1) and a feed port of the second-stage rectifying tower (2), and a gas outlet is connected with a feed port of an ammonium carbonate crystallization kettle (4);
the top of the secondary rectifying tower (2) is connected with a secondary condenser (21), a liquid discharge port of the condenser is respectively connected with the top of the secondary rectifying tower (2) and a feed inlet of an alcohol neutralization tank (5), and a gas outlet is connected with a feed inlet of an ammonium carbonate crystallization kettle (4);
an acid metering tank (51) is connected to the alcohol neutralization tank (5), and a discharge hole of the alcohol neutralization tank (5) is connected with a feed inlet of the third-stage rectifying tower (3);
the top of the third-stage rectifying tower (3) is connected with a third-stage condenser (31), part of the discharged material of the condenser reflows to the third-stage rectifying tower (3), and the rest enters an alcohol finished product tank (32);
and the first-stage condenser and the second-stage condenser are respectively provided with a heat preservation device (8) with a connecting pipeline at the top of the corresponding rectifying tower and a connecting pipeline with the ammonium carbonate crystallization kettle.
2. The apparatus for separating alcohol and ammonium carbonate in wastewater according to claim 1, wherein: the liquid discharge port of the first-stage condenser (11) is also connected with the feed port of the ammonium carbonate crystallization kettle (4).
3. The apparatus for separating alcohol and ammonium carbonate in wastewater according to claim 1, wherein: the liquid discharge port of the primary condenser (11) is connected with the primary alcohol receiving tank (12) firstly, and the liquid is discharged from the discharge port of the primary alcohol receiving tank (12); and/or:
the liquid discharge port of the secondary condenser (21) is connected with the secondary alcohol receiving tank (22) first, and the liquid is discharged from the discharge port of the secondary alcohol receiving tank (22).
4. The apparatus for separating alcohol and ammonium carbonate in wastewater according to claim 1, wherein: the discharge hole of the ammonium carbonate crystallization kettle (4) is connected with a solid-liquid separation device (41), and the top of the ammonium carbonate crystallization kettle (4) is connected with a tail gas absorption tank (43).
5. The apparatus for separating alcohol and ammonium carbonate in wastewater according to claim 4, wherein: and a liquid outlet of the solid-liquid separation equipment (41) is connected with a feed inlet of the secondary rectifying tower (2).
6. The apparatus for separating alcohol and ammonium carbonate in wastewater according to claim 5, wherein: and a liquid outlet of the solid-liquid separation equipment (41) is connected with the secondary rectifying tower (2) through an alcohol storage tank (42).
7. The apparatus for separating alcohol and ammonium carbonate in wastewater according to claim 6, wherein: the liquid outlet of the first-stage condenser (11) is also connected with the second-stage rectifying tower (2) through an alcohol storage tank (42).
8. The apparatus for separating alcohol and ammonium carbonate in wastewater according to claim 1, wherein: the primary rectifying tower (1), the secondary rectifying tower (2) and the tertiary rectifying tower (3) are packed towers, plate towers or combined towers consisting of the packed towers and the plate towers, wherein the plate towers are sieve plate towers, perforated plate towers, plate float valve towers or plate bubble towers; the number of the theoretical plates of the stripping section of the first-stage rectifying tower (1) and the second-stage rectifying tower (2) is 5-10, the number of the theoretical plates of the rectifying section is 20-30, and the number of the theoretical plates of the rectifying sections in the third-stage rectifying tower (3) is 20-30.
9. A method for separating alcohol and ammonium carbonate in wastewater using the apparatus of any one of claims 1 to 8, characterized in that:
continuously pumping wastewater containing alcohol and ammonium carbonate into a first-stage rectifying tower (1), heating and rectifying, introducing 40-50 ℃ hot water into a first-stage condenser (11) and a second-stage condenser (21), and keeping the temperature of 50-60 ℃ by using a heat preservation device (8) to ensure that the first-stage condenser (11) and the second-stage condenser (21) are respectively connected with connecting pipelines at the top of the corresponding rectifying tower and the connecting pipelines respectively connected with an ammonium carbonate crystallization kettle (4); the method comprises the following steps that residual gas phase after condensation of a first-stage condenser (11) enters an ammonium carbonate crystallization kettle (4), ammonium carbonate solid is generated through crystallization, condensed first-stage rectification alcohol enters a second-stage rectification tower (2) for rectification, residual gas phase after condensation of a second-stage condenser (21) enters the ammonium carbonate crystallization kettle (4), ammonium carbonate solid is generated through crystallization, the condensed second-stage rectification alcohol enters an alcohol neutralization tank (5), the condensed second-stage rectification alcohol enters a third-stage rectification tower (3) for rectification after neutralization to neutrality through acid, and the third-stage condenser (31) discharges to an alcohol finished product tank (32); the bottom of the first-stage rectifying tower (1) and the second-stage rectifying tower (2) is discharged to be qualified water, and the bottom of the third-stage rectifying tower (3) is discharged to be an ammonium sulfate solution.
10. The method of claim 9, wherein: the tower top temperatures of the first-stage rectifying tower (1), the second-stage rectifying tower (2) and the third-stage rectifying tower (3) are 64-80 ℃; the temperature of the tower kettle is 80-105 ℃, the pressure in the rectifying tower is 0.1 KPa-1.1 KPa, and the reflux ratio at the top of the tower is 2: 1-10: 1; and/or:
the temperature in the ammonium carbonate crystallization kettle (4) is 0-20 ℃, and the crystallization solvent is methanol or ethanol; and/or:
the acid for neutralization in the alcohol neutralization tank (5) is any one of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid and acetic acid.
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| CN112079509B (en) * | 2020-09-17 | 2022-08-30 | 河北威远生物化工有限公司 | Method for recycling waste water containing alcohol, ammonium carbonate and ammonia |
| CN114715966A (en) * | 2022-04-08 | 2022-07-08 | 广州市迈源科技有限公司 | Method for separating and purifying ammonium sulfate and ammonium dihydrogen phosphate in wastewater |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB457082A (en) * | 1936-01-07 | 1936-11-20 | Albert George Black | Improved process for the recovery of ammonium compounds from ammoniacal liquors or the like and for the manufacture of a grease solvent |
| EP0622335A1 (en) * | 1992-01-16 | 1994-11-02 | M. W. Kellogg Company | A method for treating ammonia and urea condensates |
| CN106132874A (en) * | 2014-03-21 | 2016-11-16 | 赢创罗姆有限公司 | From alcoholic solution, the method removing ammonia is separated in the presence of carbonate compound |
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2018
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB457082A (en) * | 1936-01-07 | 1936-11-20 | Albert George Black | Improved process for the recovery of ammonium compounds from ammoniacal liquors or the like and for the manufacture of a grease solvent |
| EP0622335A1 (en) * | 1992-01-16 | 1994-11-02 | M. W. Kellogg Company | A method for treating ammonia and urea condensates |
| CN106132874A (en) * | 2014-03-21 | 2016-11-16 | 赢创罗姆有限公司 | From alcoholic solution, the method removing ammonia is separated in the presence of carbonate compound |
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