CN102512931A - Method for preparing sodium hydrosulphite by utilization of tail gas from acyl chloride production - Google Patents
Method for preparing sodium hydrosulphite by utilization of tail gas from acyl chloride production Download PDFInfo
- Publication number
- CN102512931A CN102512931A CN2011104062431A CN201110406243A CN102512931A CN 102512931 A CN102512931 A CN 102512931A CN 2011104062431 A CN2011104062431 A CN 2011104062431A CN 201110406243 A CN201110406243 A CN 201110406243A CN 102512931 A CN102512931 A CN 102512931A
- Authority
- CN
- China
- Prior art keywords
- tail gas
- solution
- acyl chlorides
- sulfur dioxide
- produced
- 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.)
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Links
- 150000001263 acyl chlorides Chemical class 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 title abstract 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000000243 solution Substances 0.000 claims abstract description 27
- 238000010521 absorption reaction Methods 0.000 claims abstract description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 18
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical class [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims abstract description 17
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 9
- 238000007599 discharging Methods 0.000 claims abstract description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 50
- 239000007788 liquid Substances 0.000 claims description 31
- 229940001482 sodium sulfite Drugs 0.000 claims description 22
- 235000010265 sodium sulphite Nutrition 0.000 claims description 22
- 239000011734 sodium Substances 0.000 claims description 19
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims description 10
- 229940101006 anhydrous sodium sulfite Drugs 0.000 claims description 6
- 239000012047 saturated solution Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 abstract description 8
- 239000012527 feed solution Substances 0.000 abstract 4
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 36
- 230000009102 absorption Effects 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 15
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 7
- 238000010923 batch production Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 1
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
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- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The invention relates to a method for preparing sodium hydrosulphite by the utilization of tail gas from acyl chloride production. The method has advantages of high absorptivity of sulfur dioxide, high absorption efficiency of sulfur dioxide, good sodium hydrosulphite product quality and product quality stability. The method comprises the following steps of: (1) absorbing the tail gas from acyl chloride production through water and removing HCl gas; (2) removing a few HCl gas from sulfur dioxide by the use of a saturated sodium bisulfite solution; (3) allowing the acyl chloride production tail gas processed from the step (2) to enter into a continuous feeding and continuous discharging absorption kettle filled with a sodium carbonate solution, carrying out three-stage continuous absorption of sulfur dioxide at normal pressure at 40-110 DEG C to generate a sodium bisulfite containing feed solution, discharging the feed solution, and controlling pH of the discharged feed solution within 3.9-5.9; and (4) neutralizing the discharged feed solution from the step (3) by the use of alkali until pH is within 8.0-10.0 to obtain a neutralizer, wherein the alkali is a NaOH solution or a Na2CO3 solution.
Description
Technical field
The present invention relates to a kind of preparation method of sodium sulfite, particularly relate to a kind of acyl chlorides that utilizes and produce the method that tail gas prepares sodium sulfite.
Background technology
The handling problem of hydrogen chloride in tail gas and sulfur dioxide is the difficult problem of the sector always when utilizing the thionyl chloride method to produce acyl chlorides.Along with the continuous expansion and the fast development of China's acyl chlorides industry production scale, as the main component that acyl chlorides is produced tail gas, the processing of hydrogen chloride is relatively easy, and the processing of sulfur dioxide is then comparatively difficult.At present, water absorption method is mainly adopted in the processing of acyl chlorides production hydrogen chloride in tail gas, and the processing method of sulfur dioxide mainly contains: employing alkali lye carries out the batch process absorption and absorbs two kinds of methods with lime.Adopt alkali lye carry out batch process absorb be meant adopt batch process, with alkali lye or soda ash solution the SO 2 tail gas in the acyl chlorides production is absorbed, neutralize, concentrates and drying to prepare the method for sodium sulfite; The lime absorption process is meant the method that direct employing limewash absorbs SO 2 tail gas.Former approach has shortcomings such as the sulfur dioxide absorption efficiency is not high, unstable product quality; It then is a kind of method that falls behind relatively that lime absorbs, and its absorption rate of sulfur dioxide is not high, and the calcium sulfite use of generation is also little.
Summary of the invention
The technical problem that the present invention will solve provides the acyl chlorides that utilizes of a kind of absorption rate of sulfur dioxide height, sulfur dioxide absorption efficiency height, sodium sulfite good product quality and constant product quality and produces the method that tail gas prepares sodium sulfite.
A kind of acyl chlorides that utilizes is produced the method that tail gas prepares sodium sulfite, may further comprise the steps:
(1) acyl chlorides is produced tail gas through the water absorption, removes HCl gas wherein; Can obtain the concentrated hydrochloric acid that mass fraction is 28-32%;
(2) remove the small amount of H Cl gas that is mixed with in the sulfur dioxide with saturated solution of sodium bisulfite;
(3) acyl chlorides handled of step (2) is produced tail gas and is fed continuous feed and discharging continuously and be equipped with in the absorption still of sodium carbonate liquor under the condition of normal pressure, 40-110 ℃ and carry out three grades of continuous absorbing sulfur dioxide; Generation contains the feed liquid of sodium hydrogensulfite and emits, and the pH that feed liquid is emitted in control is 3.9-5.9; Wherein: three grades of continuous equipment therefors that absorb comprise first agitated reactor, second agitated reactor, the 3rd agitated reactor, and first to the 3rd agitated reactor links to each other through pipeline in order, and Na all is housed in each agitated reactor
2CO
3Solution, the acyl chlorides that step (2) was handled is produced tail gas and is fed first agitated reactor and Na
2CO
3Solution reaction, the SO that first agitated reactor fails to sponge
2, get into second and third agitated reactor through pipeline and absorb once more.Na in the agitated reactor
2CO
3Solution and SO
2Reaction, generation contains NaHSO
3Feed liquid, emit continuously in first agitated reactor during work and contain NaHSO
3Feed liquid, the feed liquid that first agitated reactor reduces adopts press over system to replenish Na by second agitated reactor
2CO
3Solution, second agitated reactor replenishes Na by the 3rd agitated reactor
2CO
3Solution is with the Na for preparing
2CO
3The solution continuous supplementation is in the 3rd agitated reactor; During three grades of continuous absorptions, the Na between first, second and third agitated reactor
2CO
3The pH size of feed liquid that contains sodium hydrogensulfite in solution flow rate size and first agitated reactor is relevant, controlled by automatic regulating valve, when pH that contains the sodium hydrogensulfite feed liquid in first agitated reactor and the pH that emits feed liquid control differ than greatly the time Na between agitated reactor
2CO
3Solution flow rate is big; The pH that in first agitated reactor, contains the sodium hydrogensulfite feed liquid and the pH that emits feed liquid control differ hour, the Na between agitated reactor
2CO
3Solution flow rate is little.Reaction equation is following:
Na
2CO
3+2SO
2+H
2O＝2NaHSO
3+CO
2；
(4) step (3) feed liquid of emitting neutralizes with alkali, ends for 8.0-10.0 to the pH value, obtains neutralizer, and wherein said alkali is NaOH solution or Na
2CO
3Solution.Sodium hydrogensulfite and alkali reaction generate sodium sulfite.Reaction equation is:
Na
2CO
3+2NaHSO
3＝2Na
2SO
3+CO
2+H
2O；
The present invention utilizes acyl chlorides to produce the method that tail gas prepares sodium sulfite; Wherein said step (3) is: acyl chlorides that step (2) was handled is produced tail gas and is fed continuous feed with discharging continuously and be equipped with in the absorption still of sodium carbonate liquor; Under normal pressure, 70 ℃ condition, carry out three grades of continuous absorbing sulfur dioxide; Generation contains the feed liquid of sodium hydrogensulfite and emits, and the pH that feed liquid is emitted in control is 4.9;
The present invention utilizes acyl chlorides to produce the method that tail gas prepares sodium sulfite, also comprises after the wherein said step (4) after neutralizer is through evaporative crystallization, centrifugal, drying obtaining anhydrous sodium sulfite.
The present invention utilizes acyl chlorides to produce the method that tail gas prepares sodium sulfite, wherein NaOH solution or Na described in the step (4)
2CO
3The mass fraction of solution is 30-35%.
The present invention utilizes acyl chlorides to produce the method that tail gas prepares sodium sulfite, wherein Na described in the step (3)
2CO
3The concentration of solution is 200g/L-250g/L.
The present invention utilizes acyl chlorides to produce the method that tail gas prepares sodium sulfite, and wherein said acyl chlorides is produced tail gas and absorbed three grades of falling liquid film water absorption methods of employing through water.
The present invention utilizes acyl chlorides to produce method that tail gas prepares sodium sulfite compared with prior art, and its absorption rate of sulfur dioxide reaches more than 99.8%; Produce sodium sulfite with original employing batch process and compare, the output of sodium sulfite is brought up to 11.2 tons by producing 8.3 tons original every day, has improved 35%, and the treating capacity of acyl chlorides being produced tail gas has also improved 30-40%; And product sodium sulfite purity reaches country-level standard; Compare with batch process, absorb continuously the operate miss between not having batch, product quality is more stable.
Below in conjunction with accompanying drawing the present invention is described further.
Description of drawings
Fig. 1 produces the flow chart that tail gas prepares the method for anhydrous sodium sulfite for the present invention utilizes acyl chlorides;
The specific embodiment
Embodiment 1
(1) acyl chlorides is produced tail gas through the absorption of falling liquid film water, removes HCl gas wherein, and the generation mass fraction is 30% concentrated hydrochloric acid;
(2) remove the small amount of H Cl gas that is mixed with in the sulfur dioxide with saturated solution of sodium bisulfite;
(3) acyl chlorides handled of step (2) is produced tail gas and is fed continuous feed and discharging continuously and be equipped with in the absorption still of sodium carbonate liquor that concentration is 200g/L; Under normal pressure, 40 ℃ condition, carry out three grades of continuous absorbing sulfur dioxide; Generation contains the feed liquid of sodium hydrogensulfite and emits, and the pH that feed liquid is emitted in control is 5.9;
(4) to use mass fraction be that 30% NaOH solution neutralizes to step (3) feed liquid of emitting, to pH value be 10.0 only, obtain neutralizer.
Absorptivity through above-mentioned steps sulfur dioxide reaches more than 99.8%, again with neutralizer carry out condensing crystallizing, centrifugal and dry after obtain anhydrous sodium sulfite, product reaches country-level standard.
Embodiment 2
(1) acyl chlorides is produced tail gas through the absorption of falling liquid film water, removes HCl gas wherein, and the generation mass fraction is 32% concentrated hydrochloric acid;
(2) remove the small amount of H Cl gas that is mixed with in the sulfur dioxide with saturated solution of sodium bisulfite;
(3) acyl chlorides handled of step (2) is produced tail gas and is fed continuous feed and discharging continuously and be equipped with in the absorption still of sodium carbonate liquor that concentration is 250g/L; Under normal pressure, 110 ℃ condition, carry out three grades of continuous absorbing sulfur dioxide; Generation contains the feed liquid of sodium hydrogensulfite and emits, and the pH that feed liquid is emitted in control is 3.9;
(4) to use mass fraction be 30% Na to step (3) feed liquid of emitting
2CO
3Solution neutralizes, and is 8.0 to end to the pH value, obtains neutralizer.
Absorptivity through above-mentioned steps sulfur dioxide reaches more than 99.8%, again with neutralizer carry out condensing crystallizing, centrifugal and dry after obtain anhydrous sodium sulfite, product reaches country-level standard.
Embodiment 3
(1) acyl chlorides is produced tail gas through the absorption of falling liquid film water, removes HCl gas wherein, and the generation mass fraction is 28% concentrated hydrochloric acid;
(2) remove the small amount of H Cl gas that is mixed with in the sulfur dioxide with saturated solution of sodium bisulfite;
(3) acyl chlorides handled of step (2) is produced tail gas and is fed continuous feed and discharging continuously and be equipped with in the absorption still of sodium carbonate liquor that concentration is 225g/L; Under normal pressure, 70 ℃ condition, carry out three grades of continuous absorbing sulfur dioxide; Generation contains the feed liquid of sodium hydrogensulfite and emits, and the pH that feed liquid is emitted in control is 4.9;
(4) to use mass fraction be 35% Na to step (3) feed liquid of emitting
2CO
3Solution neutralizes, and is 9.0 to end to the pH value, obtains neutralizer.
Absorptivity through above-mentioned steps sulfur dioxide reaches more than 99.8%, again with neutralizer carry out condensing crystallizing, centrifugal and dry after obtain anhydrous sodium sulfite, product reaches country-level standard.
Above-described embodiment describes preferred implementation of the present invention; Be not that scope of the present invention is limited; Design under the prerequisite of spirit not breaking away from the present invention; Various distortion and improvement that those of ordinary skills make technical scheme of the present invention all should fall in the definite protection domain of claims of the present invention.
Claims (5)
1. one kind is utilized acyl chlorides to produce the method that tail gas prepares sodium sulfite, it is characterized in that may further comprise the steps:
(1) acyl chlorides is produced tail gas through the water absorption, removes HCl gas wherein;
(2) remove the small amount of H Cl gas that is mixed with in the sulfur dioxide with saturated solution of sodium bisulfite;
(3) acyl chlorides handled of step (2) is produced tail gas and is fed continuous feed with discharging continuously and be equipped with in the absorption still of sodium carbonate liquor; Under the condition of normal pressure, 40-110 ℃, carry out three grades of continuous absorbing sulfur dioxide; Generation contains the feed liquid of sodium hydrogensulfite and emits this feed liquid, and the pH that feed liquid is emitted in control is 3.9-5.9;
(4) step (3) feed liquid of emitting neutralizes with alkali, ends for 8.0-10.0 to the pH value, obtains neutralizer, and wherein said alkali is NaOH solution or Na
2CO
3Solution.
2. the acyl chlorides that utilizes according to claim 1 is produced the method that tail gas prepares sodium sulfite, it is characterized in that: also comprise after the said step (4) after neutralizer is through evaporative crystallization, centrifugal, drying obtaining anhydrous sodium sulfite.
3. the acyl chlorides that utilizes according to claim 2 is produced the method that tail gas prepares sodium sulfite, it is characterized in that: said NaOH solution or Na
2CO
3The mass fraction of solution is 30-35%.
4. the acyl chlorides that utilizes according to claim 3 is produced the method that tail gas prepares sodium sulfite, it is characterized in that: said Na
2CO
3The concentration of solution is 200g/L-250g/L.
5. the acyl chlorides that utilizes according to claim 4 is produced the method that tail gas prepares sodium sulfite, it is characterized in that: said acyl chlorides is produced tail gas and is absorbed three grades of falling liquid film water absorption methods of employing through water.
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|---|---|---|---|
| CN201110406243.1A CN102512931B (en) | 2011-12-08 | 2011-12-08 | Method for preparing sodium hydrosulphite by utilization of tail gas from acyl chloride production |
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|---|---|---|---|
| CN201110406243.1A CN102512931B (en) | 2011-12-08 | 2011-12-08 | Method for preparing sodium hydrosulphite by utilization of tail gas from acyl chloride production |
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| Publication Number | Publication Date |
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| CN102512931A true CN102512931A (en) | 2012-06-27 |
| CN102512931B CN102512931B (en) | 2014-04-16 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102824820A (en) * | 2012-08-27 | 2012-12-19 | 安徽常泰化工有限公司 | Treatment technology for tail gas generated from production process of cis-Z-3-(2-chloro-3, 3, 3-triflulo-1-propenyl)-2, 2-dimethyl cyclopropane carbonyl chloride |
| CN102976946A (en) * | 2012-12-13 | 2013-03-20 | 烟台泰和新材料股份有限公司 | Method for synthesizing dimethyl isophthalate |
| CN102989265A (en) * | 2012-12-13 | 2013-03-27 | 烟台泰和新材料股份有限公司 | Treatment method of acyl chloride production tail gas |
| CN103332751A (en) * | 2013-05-22 | 2013-10-02 | 玉门市翔宇环保有限公司 | Ferrous sulfate comprehensive utilization method |
| CN104587822A (en) * | 2015-01-22 | 2015-05-06 | 贵州兰鑫石墨机电设备制造有限公司 | Separation device for hydrogen chloride and sulfur dioxide as well as separation method thereof |
| CN109455742A (en) * | 2019-01-06 | 2019-03-12 | 曲阜师范大学 | A kind of method of simple production pharmaceutic adjuvant anhydrous sodium sulfite |
| CN112939028A (en) * | 2020-11-03 | 2021-06-11 | 宣城市楷昂化工有限公司 | Preparation method of sodium sulfite |
| CN113003587A (en) * | 2021-03-02 | 2021-06-22 | 安徽金轩科技有限公司 | Continuous production method for recovering sodium sulfite from thionyl chloride tail gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109289481A (en) * | 2018-10-25 | 2019-02-01 | 老河口市天和科技有限公司 | Sulfonic chloride produces gas recovery system and technique |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102824820A (en) * | 2012-08-27 | 2012-12-19 | 安徽常泰化工有限公司 | Treatment technology for tail gas generated from production process of cis-Z-3-(2-chloro-3, 3, 3-triflulo-1-propenyl)-2, 2-dimethyl cyclopropane carbonyl chloride |
| CN102976946A (en) * | 2012-12-13 | 2013-03-20 | 烟台泰和新材料股份有限公司 | Method for synthesizing dimethyl isophthalate |
| CN102989265A (en) * | 2012-12-13 | 2013-03-27 | 烟台泰和新材料股份有限公司 | Treatment method of acyl chloride production tail gas |
| CN103332751A (en) * | 2013-05-22 | 2013-10-02 | 玉门市翔宇环保有限公司 | Ferrous sulfate comprehensive utilization method |
| CN103332751B (en) * | 2013-05-22 | 2015-08-26 | 玉门市翔宇环保有限公司 | Ferrous sulfate method of comprehensive utilization |
| CN104587822A (en) * | 2015-01-22 | 2015-05-06 | 贵州兰鑫石墨机电设备制造有限公司 | Separation device for hydrogen chloride and sulfur dioxide as well as separation method thereof |
| CN109455742A (en) * | 2019-01-06 | 2019-03-12 | 曲阜师范大学 | A kind of method of simple production pharmaceutic adjuvant anhydrous sodium sulfite |
| CN109455742B (en) * | 2019-01-06 | 2021-01-12 | 曲阜师范大学 | Method for simply producing pharmaceutic adjuvant anhydrous sodium sulfite |
| CN112939028A (en) * | 2020-11-03 | 2021-06-11 | 宣城市楷昂化工有限公司 | Preparation method of sodium sulfite |
| CN112939028B (en) * | 2020-11-03 | 2023-05-26 | 宣城市楷昂化工有限公司 | Preparation method of sodium sulfite |
| CN113003587A (en) * | 2021-03-02 | 2021-06-22 | 安徽金轩科技有限公司 | Continuous production method for recovering sodium sulfite from thionyl chloride tail gas |
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|---|---|
| CN102512931B (en) | 2014-04-16 |
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Address after: 264006 No. 10, Heilongjiang Road, Yantai economic and Technological Development Zone, Yantai, Shandong Patentee after: Taihe New Material Group Co.,Ltd. Patentee after: YANTAI YUXIANG FINE CHEMICAL Co.,Ltd. Address before: 264006 No. 10, Heilongjiang Road, Yantai economic and Technological Development Zone, Yantai, Shandong Patentee before: YANTAI TAYHO ADVANCED MATERIALS Co.,Ltd. Patentee before: YANTAI YUXIANG FINE CHEMICAL Co.,Ltd. |
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Effective date of registration: 20231213 Address after: 750411 Ningxia Ningdong Energy and Chemical Base Coal Chemical Industry Park, Yinchuan City, Ningxia Hui Autonomous Region, north of Yinglite Project Park Road and east of parking lot Patentee after: Ningxia Ningdong Taihe Chemical Technology Co.,Ltd. Patentee after: Taihe New Material Group Co.,Ltd. Address before: 264006 No. 10, Heilongjiang Road, Yantai economic and Technological Development Zone, Yantai, Shandong Patentee before: Taihe New Material Group Co.,Ltd. Patentee before: YANTAI YUXIANG FINE CHEMICAL Co.,Ltd. |