TWI481549B - Method for preparing sulfur trioxide from recovered waste sulfuric acid and device for continuously manufacturing sulfur trioxide - Google Patents
Method for preparing sulfur trioxide from recovered waste sulfuric acid and device for continuously manufacturing sulfur trioxide Download PDFInfo
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims description 372
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 title claims description 156
- 239000002699 waste material Substances 0.000 title claims description 59
- 238000000034 method Methods 0.000 title claims description 44
- 238000004519 manufacturing process Methods 0.000 title description 6
- 238000006243 chemical reaction Methods 0.000 claims description 92
- 238000010521 absorption reaction Methods 0.000 claims description 57
- 239000012024 dehydrating agents Substances 0.000 claims description 38
- 239000007788 liquid Substances 0.000 claims description 29
- 238000004821 distillation Methods 0.000 claims description 25
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims description 25
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 17
- 239000012498 ultrapure water Substances 0.000 claims description 17
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 238000006297 dehydration reaction Methods 0.000 claims description 13
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 11
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 9
- 238000005292 vacuum distillation Methods 0.000 claims description 9
- AFINAILKDBCXMX-PBHICJAKSA-N (2s,3r)-2-amino-3-hydroxy-n-(4-octylphenyl)butanamide Chemical compound CCCCCCCCC1=CC=C(NC(=O)[C@@H](N)[C@@H](C)O)C=C1 AFINAILKDBCXMX-PBHICJAKSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 4
- 238000010533 azeotropic distillation Methods 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- 238000000895 extractive distillation Methods 0.000 claims description 3
- 238000004508 fractional distillation Methods 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 238000000066 reactive distillation Methods 0.000 claims description 3
- 238000001577 simple distillation Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 26
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 235000010269 sulphur dioxide Nutrition 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- FECNOIODIVNEKI-UHFFFAOYSA-N 2-[(2-aminobenzoyl)amino]benzoic acid Chemical class NC1=CC=CC=C1C(=O)NC1=CC=CC=C1C(O)=O FECNOIODIVNEKI-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000004291 sulphur dioxide Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Description
本發明係關於一種自回收之廢硫酸製備三氧化硫之方法及連續製造三氧化硫之裝置；特別關於一種利用磷酸衍生物等脫水劑對該廢硫酸進行脫水而製備三氧化硫之方法及可連續製造三氧化硫之裝置。The invention relates to a method for preparing sulfur trioxide from self-recovered waste sulfuric acid and a device for continuously manufacturing sulfur trioxide; in particular, a method for preparing sulfur trioxide by dehydrating the waste sulfuric acid with a dehydrating agent such as a phosphoric acid derivative and A device for continuously producing sulfur trioxide.
近年來隨著半導體或電子科技業的急遽發展，連帶使製程中用於晶圓清洗或面板蝕刻之硫酸液用量大幅提升，進一步造成廢硫酸產量逐年增加，該等廢硫酸若未適當處理，則會影響環境生態。In recent years, with the rapid development of the semiconductor or electronic technology industry, the amount of sulfuric acid liquid used for wafer cleaning or panel etching in the process has been greatly increased, which further increases the production of waste sulfuric acid every year. If the waste sulfuric acid is not properly treated, Will affect the environment and ecology.
現今廢硫酸的回收應用，最常見者為對廢硫酸進行純化精製，如日本專利特開平5-161801、特開平10-017306及特開2002-68715，係將硫酸饋入蒸餾塔進行精製處理；日本專利特開8-073206號係將硫加入含過氧化氫之廢硫酸中，於高溫下在硫存在下使過氧化氫分解而去除過氧化氫；日本專利特開平9-315806號則於含硫酸及過氧化氫之廢硫酸中投入亞硫酸，使亞硫酸與過氧化氫反應使過氧化氫分解同時生成硫酸而以硫酸溶液回收廢液。由上可見，目前工業上對於廢硫酸的回收，大部分在於脫去廢硫酸中的過氧化氫，而能進一步得到精製硫酸。Nowadays, the most common recycling of waste sulfuric acid is the purification and purification of waste sulfuric acid. For example, Japanese Patent Laid-Open No. Hei 5-161801, Japanese Patent Application Laid-Open No. Hei 10-017306, and No. 2002-68715, the sulfuric acid is fed into a distillation column for refining treatment; Japanese Patent Laid-Open No. 8-073206 incorporates sulfur into waste sulfuric acid containing hydrogen peroxide, and decomposes hydrogen peroxide in the presence of sulfur at a high temperature to remove hydrogen peroxide; Japanese Patent Laid-Open No. 9-315806 contains Sulfuric acid is added to the spent sulfuric acid of sulfuric acid and hydrogen peroxide, and sulfurous acid is reacted with hydrogen peroxide to decompose the hydrogen peroxide to form sulfuric acid, and the waste liquid is recovered as a sulfuric acid solution. It can be seen from the above that most of the industrial recovery of waste sulfuric acid is to remove the hydrogen peroxide in the waste sulfuric acid, and further obtain refined sulfuric acid.
硫酸係可製備成其他形態，如可將三氧化硫氣體打入硫酸中，而製成發煙硫酸(H2 SO4 .xSO3 )，其主要可作為磺化或硝化反應的脫水劑，並可廣泛用於炸藥、石油、染料中間體、塑料、合成纖維、合成吸收劑或藥物等生產的用途。而發煙硫酸之製備方式則如美國專利公開號第US 2003077217、美國專利號第US 5,389,354等所揭示者，都是以含釩觸媒接觸法於350至500℃下，將二氧化硫轉換為三氧化硫，接著於吸收塔中以濃硫酸吸收三氧化硫以製備發煙硫酸，其中二氧化硫的來源皆以硫磺為原料燃 燒製備而得。The sulfuric acid system can be prepared into other forms, such as sulfur trioxide gas can be driven into sulfuric acid to form fuming sulfuric acid (H 2 SO 4 .xSO 3 ), which can be mainly used as a dehydrating agent for sulfonation or nitration reaction, and It can be widely used in the production of explosives, petroleum, dye intermediates, plastics, synthetic fibers, synthetic absorbents or pharmaceuticals. The sulphuric acid is prepared by converting the sulphur dioxide to trioxide at a temperature of 350 to 500 ° C by a vanadium-containing catalyst contact method, as disclosed in U.S. Patent Publication No. US 2003077217, and U.S. Patent No. 5,389,354. Sulfur, followed by absorption of sulfur trioxide by concentrated sulfuric acid in an absorption tower to prepare fuming sulfuric acid, wherein the source of sulfur dioxide is prepared by burning sulfur as a raw material.
綜上所述，目前產業上仍缺一種不需觸媒反應且可於低溫、低成本條件下利用回收之廢硫酸製備三氧化硫之方法。In summary, the industry still lacks a method for preparing sulfur trioxide using recycled sulfuric acid at low temperature and low cost without the need of a catalyst reaction.
鑒於上述問題，本發明一方面係提供一種自回收之廢硫酸製備三氧化硫之方法，該方法包括：使廢硫酸與選自由焦磷酸、偏磷酸及多聚磷酸所組成之群組之至少一種磷酸衍生物脫水劑，於溫度為100至350℃之範圍、絕對壓力為0.1 mmHg至10 atm之範圍下，進行硫酸脫水反應而產出三氧化硫；其中相對於廢硫酸所含之硫酸每重量份，脫水劑使用量為1.0至10.0重量份。依據本發明之方法，由於其係自廢硫酸中製備三氧化硫，而不必額外添加含硫物質，故而可達到省能源及資源再利用的優點，且由於所使用之脫水劑為液態而為相容性及處理性良好，因而可便於本發明之三氧化硫之製法工業化；再者，由於整體反應可在較低溫度進行，而可大幅降低習知三氧化硫製程中因高溫所帶來的危險性，且可減少設備成本。In view of the above problems, an aspect of the present invention provides a method for preparing sulfur trioxide from recovered spent sulfuric acid, the method comprising: at least one selected from the group consisting of pyrophosphoric acid, metaphosphoric acid, and polyphosphoric acid. a dehydrating agent for a phosphoric acid derivative, which is subjected to a dehydration reaction of sulfuric acid to produce sulfur trioxide at a temperature ranging from 100 to 350 ° C and an absolute pressure of from 0.1 mmHg to 10 atm; wherein the sulfuric acid per weight is equivalent to that of the spent sulfuric acid The dehydrating agent is used in an amount of 1.0 to 10.0 parts by weight. According to the method of the present invention, since sulfur trioxide is prepared from waste sulfuric acid without additional sulfur-containing substances, the advantages of energy saving and resource recycling can be achieved, and the dehydrating agent used is liquid due to the use of the dehydrating agent. Good capacity and handleability, thus facilitating the industrialization of the sulfur trioxide method of the present invention; furthermore, since the overall reaction can be carried out at a lower temperature, the high temperature in the conventional sulfur trioxide process can be greatly reduced. Hazard and reduce equipment costs.
依據本發明之方法，其中該廢硫酸於進行脫水反應前先經濃縮處理而得工業級硫酸，且其中該濃縮係使用蒸餾法、薄膜分離法或電解法；其中，該蒸餾法可為分餾、簡單蒸餾、共沸蒸餾、變壓蒸餾、萃取蒸餾、反應蒸餾或減壓蒸餾，較佳係於反應溫度50至350℃、絕對壓力0.1 mmHg至750 mmHg下，使該廢硫酸進行減壓蒸餾濃縮；濃縮後所得之工業級硫酸濃度為50%至98%，較佳為80%至98%，最佳為90%至98%。According to the method of the present invention, the spent sulfuric acid is subjected to concentration treatment before being subjected to a dehydration reaction to obtain industrial grade sulfuric acid, and wherein the concentration is performed by distillation, membrane separation or electrolysis; wherein the distillation may be fractional distillation, Simple distillation, azeotropic distillation, pressure swing distillation, extractive distillation, reactive distillation or vacuum distillation, preferably at a reaction temperature of 50 to 350 ° C, an absolute pressure of 0.1 mmHg to 750 mmHg, and the waste sulfuric acid is subjected to vacuum distillation and concentration. The concentration of the industrial grade sulfuric acid obtained after concentration is from 50% to 98%, preferably from 80% to 98%, most preferably from 90% to 98%.
於本發明之一較佳實施例中，其中於硫酸與磷酸衍生物反應產生三氧化硫後產生之副產物磷酸，可透過熱分解除水而回復為流體性質的焦磷酸、偏磷酸或多聚磷酸，從而可將該焦磷酸、偏磷酸或多聚磷酸重複使用於使硫酸脫水製造三氧化硫之製程中，而可達成重複使用脫水劑的優點。In a preferred embodiment of the present invention, the by-product phosphoric acid produced by the reaction of sulfuric acid with a phosphoric acid derivative to produce sulfur trioxide can be returned to the hydrolyzed pyrophosphoric acid, metaphosphoric acid or polycondensation by heat separation. Phosphoric acid, so that the pyrophosphoric acid, metaphosphoric acid or polyphosphoric acid can be repeatedly used in the process of dehydrating sulfuric acid to produce sulfur trioxide, and the advantage of reusing the dehydrating agent can be achieved.
再者，本發明之方法所製備之三氧化硫可進一步於吸收塔中，經工業級硫酸吸收而製得發煙硫酸；其中該饋入吸收塔中之工業級硫酸較佳係由該廢硫酸經濃縮後而製得者。Furthermore, the sulfur trioxide prepared by the method of the present invention can be further obtained in the absorption tower by industrial grade sulfuric acid to obtain fuming sulfuric acid; wherein the industrial grade sulfuric acid fed into the absorption tower is preferably made of the waste sulfuric acid. Made after concentration.
或者，本發明之方法所製備之三氧化硫可進一步於吸收塔中，經硫酸濃度為96%以上之所謂電子級硫酸吸收而製得電子級發煙硫酸； 其中該所製得之電子級發煙硫酸可進一步加入超純水稀釋而製得電子級硫酸，並可將該電子級硫酸分流，再饋入吸收塔中重複吸收三氧化硫，因此可於製程中重複使用，即可無需再額外加購電子級硫酸。Alternatively, the sulfur trioxide prepared by the method of the present invention can be further obtained in an absorption tower by absorption of so-called electronic grade sulfuric acid having a sulfuric acid concentration of 96% or more to obtain electronic grade fuming sulfuric acid; The electronic grade fuming sulfuric acid prepared by the method can be further diluted with ultrapure water to prepare electronic grade sulfuric acid, and the electronic grade sulfuric acid can be split and fed into the absorption tower to repeatedly absorb sulfur trioxide, so that the process can be processed. Repeated use eliminates the need for additional electronic grade sulfuric acid.
本發明之另一方面係提供一種連續製造三氧化硫之裝置，其包括：一第一反應槽，用於使廢硫酸與選自由焦磷酸、偏磷酸及多聚磷酸所組成之群組之至少一種磷酸衍生物脫水劑進行脫水反應；該第一反應槽分別連接一廢硫酸進料管、一脫水劑進料管、一三氧化硫出料管，及一第一反應槽槽底液出料管，該第一反應槽槽底液出料管係出料硫酸與磷酸衍生物反應產生三氧化硫後產生之副產物磷酸；及一第二反應槽，其係於槽頂與該第一反應槽槽底液出料管連接，用於接收來自該第一反應槽槽底液並進行加熱脫水而回收該脫水劑；該第二反應槽係分別與該第一反應槽槽底液出料管、一第二反應槽出料管(出料成分為磷酸熱分解除水後之流體性質脫水劑)以及一第二反應槽槽底液出料管連接(其中該第二反應槽槽底液出料管的出料成分為主要為含有重沸物或不純物的廢酸，該廢酸可以為磷酸、焦磷酸或偏磷酸等磷酸衍生物，最後則排至廢酸收集槽進行廢液處理)，且其中該第二反應槽出料管又連接於該第一反應槽以將該回收之脫水劑饋入該第一反應槽中。Another aspect of the present invention provides a device for continuously producing sulfur trioxide, comprising: a first reaction tank for at least a waste sulfuric acid and at least one selected from the group consisting of pyrophosphoric acid, metaphosphoric acid, and polyphosphoric acid. a dehydration reaction of a phosphoric acid derivative is carried out; the first reaction tank is respectively connected with a waste sulfuric acid feed pipe, a dehydrating agent feed pipe, a sulfur trioxide discharge pipe, and a first reaction tank bottom liquid discharge a first reaction tank bottom liquid discharge pipe is a by-product phosphoric acid produced by reacting sulfuric acid with a phosphoric acid derivative to produce sulfur trioxide; and a second reaction tank connected to the top of the tank and the first reaction a tank bottom liquid discharge pipe is connected for receiving the bottom liquid from the first reaction tank and heating and dehydrating to recover the dehydrating agent; the second reaction tank is respectively connected with the first reaction tank bottom liquid discharge pipe a second reaction tank discharge pipe (the discharge component is a fluid nature dehydrating agent after the phosphoric acid heat is removed from the water) and a second reaction tank bottom liquid discharge pipe connection (where the second reaction tank bottom liquid is discharged) The discharge component of the feed tube is mainly containing a reboil or not The waste acid of the substance, the waste acid may be a phosphoric acid derivative such as phosphoric acid, pyrophosphoric acid or metaphosphoric acid, and finally discharged to a waste acid collection tank for waste liquid treatment, and wherein the second reaction tank discharge pipe is connected to the The first reaction tank feeds the recovered dehydrating agent into the first reaction tank.
本發明之裝置中，其中該廢硫酸進料管途中又可配置一蒸餾塔；藉此，可先將廢硫酸經由蒸餾塔中蒸餾，進而得到純度較高之工業級硫酸後再饋入第一反應槽中。In the device of the present invention, a distillation column can be disposed in the waste sulfuric acid feed pipe; thereby, the waste sulfuric acid can be first distilled through the distillation column to obtain the higher purity industrial grade sulfuric acid and then fed to the first In the reaction tank.
本發明之裝置中，其中該三氧化硫出料管進一步與一吸收塔連接；藉此，於該第一反應槽中所產生之三氧化硫產物可饋入吸收塔中，同時該吸收塔可進一步與一硫酸進料管連接；於本發明之一較佳實施例中，其中該硫酸進料管可為廢硫酸進料管途中配置有蒸餾塔之後段廢硫酸進料管分支後之硫酸進料管；藉此，可提供經蒸餾後的工業級硫酸至該吸收塔中與吸收塔中之三氧化硫反應，而得以產出發煙硫酸。In the apparatus of the present invention, the sulfur trioxide discharge pipe is further connected to an absorption tower; whereby the sulfur trioxide product produced in the first reaction tank can be fed into the absorption tower, and the absorption tower can be Further connected to a sulfuric acid feed pipe; in a preferred embodiment of the present invention, the sulfuric acid feed pipe may be a sulfuric acid feed pipe after the waste sulfuric acid feed pipe is disposed in the waste sulfuric acid feed pipe The material tube; thereby, the distilled industrial grade sulfuric acid can be supplied to the absorption tower to react with the sulfur trioxide in the absorption tower to produce the starting sulfuric acid.
此外，於本發明之裝置中，其中該吸收塔可進一步與一第二硫酸進料管連接，而由該第二硫酸進料管中饋入電子級硫酸；藉此，可提供電子級硫酸於該吸收塔中吸收三氧化硫反應，而得以產出電子級發煙硫酸；此外，該吸收塔可進一步具有一硫酸出料管，而該硫酸出料管係與 一超純水進料管連接以饋入超純水，其中該超純水可將吸收塔出料的電子級發煙硫酸稀釋成電子級硫酸，且該硫酸出料管之後段係可分流回該吸收塔，使該經超純水稀釋後所製備而得之電子級硫酸可進一步分流回到吸收塔，進一步於吸收塔內吸收三氧化硫以持續製備電子級發煙硫酸。Further, in the apparatus of the present invention, wherein the absorption tower is further connected to a second sulfuric acid feed pipe, and the second sulfuric acid feed pipe is fed with electronic grade sulfuric acid; thereby, electronic grade sulfuric acid can be supplied The absorption tower absorbs the sulfur trioxide reaction to produce the electronic grade fuming sulfuric acid; in addition, the absorption tower may further have a sulfuric acid discharge pipe, and the sulfuric acid discharge pipe system An ultrapure water feed pipe is connected to feed ultrapure water, wherein the ultrapure water can dilute the electronic grade fuming sulfuric acid discharged from the absorption tower into electronic grade sulfuric acid, and the sulfuric acid discharge pipe can be shunted back The absorption tower allows the electronic grade sulfuric acid prepared by diluting the ultrapure water to be further branched back to the absorption tower, and further absorbs sulfur trioxide in the absorption tower to continuously prepare the electronic grade fuming sulfuric acid.
1‧‧‧第一反應槽1‧‧‧First reaction tank
2‧‧‧第二反應槽2‧‧‧Second reaction tank
3‧‧‧廢硫酸進料管3‧‧‧Waste sulfuric acid feed pipe
3’‧‧‧廢硫酸進料管3'‧‧‧Waste sulfuric acid feed pipe
4‧‧‧脫水劑進料管4‧‧‧Dehydrator feed tube
5‧‧‧三氧化硫出料管5‧‧‧ sulfur trioxide discharge pipe
6‧‧‧第一反應槽槽底液出料管6‧‧‧First reaction tank bottom liquid discharge pipe
7‧‧‧第二反應槽出料管7‧‧‧Second reaction tank discharge pipe
8‧‧‧第二反應槽槽底液出料管8‧‧‧Second reaction tank bottom liquid discharge pipe
9‧‧‧吸收塔9‧‧‧ absorption tower
10‧‧‧蒸餾塔10‧‧‧Distillation tower
11‧‧‧硫酸進料管11‧‧‧ sulfuric acid feed tube
圖1：本發明之連續製造三氧化硫之裝置示意圖。Figure 1 is a schematic view of the apparatus for continuously producing sulfur trioxide of the present invention.
本發明一方面的主要目的是由廢硫酸中製備三氧化硫的方法，進一步而言，本發明改良了以往製備發煙硫酸時所需的三氧化硫時，必須利用含釩觸媒接觸法於350至500℃之溫度範圍，將二氧化硫轉換為三氧化硫之高溫製程，此外，更解決了半導體工業中對於廢硫酸處理的問題。其解決方法是使廢硫酸與選自由焦磷酸、偏磷酸及多聚磷酸所組成之群組之至少一種磷酸衍生物脫水劑，於溫度在100至350℃之範圍、絕對壓力在0.1 mmHg至10 atm之範圍下，進行硫酸之脫水反應而產出三氧化硫；其中相對於廢硫酸中所含硫酸每1重量份，脫水劑之使用量為1.0至10.0重量份。本發明方法於後述更詳細加以說明。The main object of one aspect of the present invention is a method for preparing sulfur trioxide from spent sulfuric acid. Further, the present invention improves the sulfur trioxide required for the preparation of fuming sulfuric acid in the past, and must utilize a vanadium-containing catalyst contact method. The temperature range of 350 to 500 ° C, the high temperature process of converting sulfur dioxide into sulfur trioxide, in addition, solves the problem of waste sulfuric acid treatment in the semiconductor industry. The solution is to make waste sulfuric acid and at least one phosphoric acid derivative dehydrating agent selected from the group consisting of pyrophosphoric acid, metaphosphoric acid and polyphosphoric acid at a temperature in the range of 100 to 350 ° C and an absolute pressure in the range of 0.1 mmHg to 10 In the range of atm, the dehydration reaction of sulfuric acid is carried out to produce sulfur trioxide; wherein the dehydrating agent is used in an amount of 1.0 to 10.0 parts by weight per 1 part by weight of the sulfuric acid contained in the spent sulfuric acid. The method of the present invention will be described in more detail later.
本發明所使用之起始原料廢硫酸，係為半導體業晶圓清洗或面板蝕刻後所產生的廢硫酸，也可以是一般工業如冶金、金屬加工業、石油工業、氯鹼工業、無機鹽工業、煉焦化學工業、電鍍業、製革業、顏料工業、橡膠工業、造紙工業、油漆工業或鉛蓄電池製造業等產出的稀硫酸或濃硫酸廢液。The starting material waste sulfuric acid used in the invention is waste sulfuric acid produced by wafer cleaning or panel etching in the semiconductor industry, and can also be general industries such as metallurgy, metal processing industry, petroleum industry, chlor-alkali industry, inorganic salt industry, Dilute sulfuric acid or concentrated sulfuric acid waste liquid produced by the coking chemical industry, electroplating industry, leather industry, pigment industry, rubber industry, paper industry, paint industry or lead storage battery manufacturing.
該廢硫酸原料為含有10%至90%硫酸及10%至90%水分，且依據廢硫酸原料來源而定，亦可能進而含有0%以上至20%之過氧化氫者，該廢硫酸可不經濃縮或純化程序，即可作為本方法之原料。但其中之雜質(主要為水或過氧化氫等雜質)可能會對製程產生影響，可經由濃縮之輔助方式減少雜質對製程所致之影響。其中，該濃縮係可使用但不限於蒸餾法、薄膜分離法或電解法；若採用蒸餾法，又可使用分餾、簡單蒸餾、共沸蒸餾、變壓蒸餾、萃取蒸餾、反應蒸餾或減壓蒸餾法。其中，以減壓蒸餾法為佳，其減壓蒸餾之反應溫度50至350℃，較佳為80至270℃，最佳 為130至250℃；減壓蒸餾之反應壓力為絕對壓力0.1 mmHg至750 mmHg下、較佳為絕對壓力1 mmHg至750 mmHg，最佳為30 mmHg至750 mmHg下。廢硫酸經濃縮後所得之工業級硫酸濃度通常為50%至98%，較佳為80%至98%，最佳為90至98%。本文中術語「工業級硫酸」係指將除去廢硫酸中水分及雙氧水等成分者，且硫酸濃度為50%至98%。The waste sulfuric acid raw material is 10% to 90% sulfuric acid and 10% to 90% moisture, and may further contain 0% or more to 20% hydrogen peroxide according to the source of the waste sulfuric acid raw material, and the waste sulfuric acid may not be used. The concentration or purification procedure can be used as a raw material for the process. However, impurities (mainly impurities such as water or hydrogen peroxide) may affect the process, and the effect of impurities on the process may be reduced by means of concentration. Wherein, the concentration system can be used but is not limited to distillation, membrane separation or electrolysis; if distillation is used, fractional distillation, simple distillation, azeotropic distillation, pressure swing distillation, extractive distillation, reactive distillation or vacuum distillation can be used. law. Among them, a vacuum distillation method is preferred, and the reaction temperature of the vacuum distillation is 50 to 350 ° C, preferably 80 to 270 ° C, preferably. The reaction pressure under reduced pressure is from 0.1 mmHg to 750 mmHg, preferably from 1 mmHg to 750 mmHg, and most preferably from 30 mmHg to 750 mmHg. The concentration of the industrial grade sulfuric acid obtained after concentration of the spent sulfuric acid is usually from 50% to 98%, preferably from 80% to 98%, most preferably from 90 to 98%. The term "industrial grade sulfuric acid" as used herein refers to a component which removes moisture and hydrogen peroxide in waste sulfuric acid, and has a sulfuric acid concentration of 50% to 98%.
本發明中所使用的脫水劑成分，係為液態之選自由焦磷酸、偏聯酸及多聚磷酸所組成之群組之至少一種，因係屬液態成分之脫水劑，故而相溶性及處理性優異，可便於本發明之三氧化硫之製法工業化；其中，相對於廢硫酸中所含之硫酸每1重量份，脫水劑之使用量為1.0至10.0重量份，較佳為2.0至9.0重量份，最佳為5.0至8.0重量份。該脫水反應之反應溫度為約100至350℃之範圍，較佳為200至350℃之範圍，最佳為270至350℃之範圍；脫水反應之反應壓力為絕對壓力0.1 mmHg至10 atm之範圍、較佳為絕對壓力50 mmHg至5 atm之範圍，最佳為100 mmHg至1 atm之範圍。The dehydrating agent component used in the present invention is at least one selected from the group consisting of pyrophosphoric acid, a dibasic acid, and a polyphosphoric acid, and is a dehydrating agent of a liquid component, so compatibility and handling property. It is excellent to facilitate the industrialization of the sulfur trioxide according to the present invention; wherein the dehydrating agent is used in an amount of 1.0 to 10.0 parts by weight, preferably 2.0 to 9.0 parts by weight per 1 part by weight of the sulfuric acid contained in the spent sulfuric acid. It is preferably 5.0 to 8.0 parts by weight. The reaction temperature of the dehydration reaction is in the range of about 100 to 350 ° C, preferably in the range of 200 to 350 ° C, preferably in the range of 270 to 350 ° C; and the reaction pressure in the dehydration reaction is in the range of 0.1 mmHg to 10 atm in absolute pressure. Preferably, it is in the range of from 50 mmHg to 5 atm, preferably from 100 mmHg to 1 atm.
依據本發明之方法，硫酸經由脫水劑脫水後所產生的三氧化硫產率通常為30%至98%，較佳為50%至98%，最佳為70%至98%；而反應後殘餘之脫水劑吸水後之副產物可進一步經收集並經加熱再度脫水後，再生產生脫水劑，而可進一步饋入本發明方法再次作為脫水劑使用。According to the method of the present invention, the sulfur trioxide produced by dehydration of sulfuric acid via a dehydrating agent is usually from 30% to 98%, preferably from 50% to 98%, most preferably from 70% to 98%; The by-product of the dehydrating agent after water absorption can be further collected and heated to be dehydrated again, and then regenerated to produce a dehydrating agent, which can be further fed into the method of the present invention and used again as a dehydrating agent.
再者，反應後所得到的三氧化硫，可進一步視需要，經工業級硫酸吸收而製得發煙硫酸。該所使用之工業級硫酸，可採用該廢硫酸於脫水反應前先經濃縮處理而得工業級硫酸，亦即該經蒸餾塔蒸餾後所產出的工業級硫酸可分流至該吸收塔作為吸收三氧化硫之用。所製得的發煙硫酸其三氧化硫的游離濃度為10%至50%，較佳為15%至40%，最佳為20%至30%。Further, the sulfur trioxide obtained after the reaction may be further subjected to industrial grade sulfuric acid absorption as needed to obtain fuming sulfuric acid. The industrial grade sulfuric acid used in the process can be obtained by concentration treatment of the waste sulfuric acid before dehydration to obtain industrial grade sulfuric acid, that is, the industrial grade sulfuric acid produced by the distillation of the distillation column can be branched to the absorption tower as absorption. Used for sulfur trioxide. The fumed sulfuric acid produced has a free concentration of sulfur trioxide of from 10% to 50%, preferably from 15% to 40%, most preferably from 20% to 30%.
或者，反應後所得到的三氧化硫，可以經濃度96%以上之電子級硫酸吸收三氧化硫而製得電子級發煙硫酸。本文中術語「電子級硫酸」係指高純度硫酸，其中所含的金屬含量皆小於1 ppb，並且泛用於對微量金屬嚴格要求的半導體產業晶圓清洗液用途上，檢測方式為利用ICP-MS儀器進行金屬含量分析；所製備所得之電子級發煙硫酸可進一步使用超純水稀釋後得到電子級硫酸，而該電子級硫酸可進一步於吸收塔內吸收三氧 化硫以持續製備電子級發煙硫酸。Alternatively, the sulfur trioxide obtained after the reaction may be subjected to absorption of sulfur trioxide by an electronic grade sulfuric acid having a concentration of 96% or more to obtain an electronic grade fuming sulfuric acid. The term "electronic grade sulfuric acid" as used herein refers to high-purity sulfuric acid, which contains less than 1 ppb of metal, and is widely used in the semiconductor industry wafer cleaning solution where trace metals are strictly required. The detection method is ICP- The MS instrument performs metal content analysis; the prepared electronic grade fuming sulfuric acid can be further diluted with ultrapure water to obtain electronic grade sulfuric acid, and the electronic grade sulfuric acid can further absorb trioxane in the absorption tower. Sulfur is used to continuously prepare electronic grade fuming sulfuric acid.
本發明之製造三氧化硫之方法可利用之裝置，如圖1所示，其包括：一第一反應槽(1)，用於使硫酸與選自由焦磷酸、偏磷酸及多聚磷酸所組成之群組之脫水劑進行脫水反應；該第一反應槽(1)分別連接一廢硫酸進料管(3)、一脫水劑進料管(4)、一三氧化硫出料管(5)，及一第一反應槽槽底液出料管(6)；及一第二反應槽(2)，用於接收來自該第一反應槽槽底液並進行加熱脫水而回收該脫水劑；該第二反應槽(2)係分別與一第一反應槽槽底液出料管(6)、一第二反應槽出料管(7)及一第二反應槽槽底液出料管(8)連接，且其中該第二反應槽出料管(7)又連接於該第一反應槽(1)以將該回收脫水劑饋入該第一反應槽(1)。藉此，三氧化硫生成後的副產物(即脫水劑反應後之已吸水之副產物)，可透過熱分解除水而使該使用過之脫水劑再生，依此不斷循環至該第一反應槽(1)中。The apparatus for producing sulfur trioxide according to the present invention can be utilized, as shown in FIG. 1, which comprises: a first reaction tank (1) for synthesizing sulfuric acid and selected from pyrophosphoric acid, metaphosphoric acid and polyphosphoric acid. The dehydrating agent of the group is subjected to a dehydration reaction; the first reaction tank (1) is respectively connected with a waste sulfuric acid feed pipe (3), a dehydrating agent feed pipe (4), and a sulfur trioxide discharge pipe (5) And a first reaction tank bottom liquid discharge pipe (6); and a second reaction tank (2) for receiving the bottom liquid from the first reaction tank and performing heat dehydration to recover the dehydrating agent; The second reaction tank (2) is respectively connected to a first reaction tank bottom liquid discharge pipe (6), a second reaction tank discharge pipe (7) and a second reaction tank bottom liquid discharge pipe (8). Connected, and wherein the second reaction tank discharge pipe (7) is in turn connected to the first reaction tank (1) to feed the recovered dehydrating agent into the first reaction tank (1). Thereby, the by-product after the formation of sulfur trioxide (that is, the by-product of water absorption after the reaction of the dehydrating agent) can regenerate the used dehydrating agent by releasing the water by heat, and thereby continuously circulate to the first reaction. In the slot (1).
在本發明之裝置中，該廢硫酸進料管(3)途中又可配置一蒸餾塔(10)，亦即該硫酸進料管(3)可分成前段之廢硫酸進料管(3’)而與蒸餾塔(10)相接，及後段之廢硫酸進料管(即相等於圖中之廢硫酸進料管(3))，係將自蒸餾塔(10)濃縮之硫酸饋入第一反應槽(1)。藉此，將廢硫酸饋入第一反應槽(1)之前，可預先使廢硫酸經由蒸餾塔(10)中蒸餾，進而得到純度較高且除去水分及/或過氧化氫等成分之工業級硫酸後再饋入第一反應槽(1)中。In the apparatus of the present invention, a distillation column (10) may be disposed in the middle of the waste sulfuric acid feed pipe (3), that is, the sulfuric acid feed pipe (3) may be divided into a waste sulfuric acid feed pipe (3') in the preceding stage. And the waste sulfuric acid feed pipe (that is equivalent to the waste sulfuric acid feed pipe (3) in the figure) connected to the distillation column (10), and the sulfuric acid concentrated from the distillation column (10) is fed into the first Reaction tank (1). Thereby, before the waste sulfuric acid is fed into the first reaction tank (1), the waste sulfuric acid can be distilled in advance through the distillation column (10), thereby obtaining an industrial grade having high purity and removing components such as moisture and/or hydrogen peroxide. The sulfuric acid is then fed into the first reaction tank (1).
再者，本發明裝置中，該三氧化硫出料管(5)又可進一步與一吸收塔(9)連接；藉此，於該第一反應槽(1)中所得到的三氧化硫產物可饋入該吸收塔(9)中，該吸收塔(9)又可進一步與一硫酸進料管(11)連接，該硫酸進料管(11)可為另外連接，亦可為自廢硫酸進料管(3)分支後之硫酸進料管；藉此，可於該吸收塔(9)中使硫酸吸收三氧化硫，而得以產出發煙硫酸。Furthermore, in the apparatus of the present invention, the sulfur trioxide discharge pipe (5) may be further connected to an absorption tower (9); thereby, the sulfur trioxide product obtained in the first reaction tank (1) It can be fed into the absorption tower (9). The absorption tower (9) can be further connected to a sulfuric acid feed pipe (11). The sulfuric acid feed pipe (11) can be connected separately or can be self-depleted sulfuric acid. The sulfuric acid feed pipe after branching of the feed pipe (3); thereby, sulfuric acid can be absorbed in the absorption tower (9) to produce sulfuric acid.
再者，該吸收塔(9)可進一步與一第二硫酸進料管(圖中未示)連接，而由該第二硫酸進料管中饋入電子級硫酸；藉此，可提供電子級硫酸於該吸收塔中(9)吸收三氧化硫，而得以產出電子級發煙硫酸；此外，該吸收塔可進一步具有一硫酸出料管(圖中未示)，而該硫酸出料管係與一超純水進料管(圖中未示)連接以饋入超純水，其中該超純水可將吸收塔出料的電子級發煙硫酸稀釋成電子級硫酸，且該硫酸出料管之後段係可分流回該吸收塔，使該經超純水稀釋後所製備而得之電子級硫酸可進一步分流回到吸 收塔，進一步於吸收塔內吸收三氧化硫以持續製備電子級發煙硫酸。Furthermore, the absorption tower (9) can be further connected to a second sulfuric acid feed pipe (not shown), and the second sulfuric acid feed pipe is fed with electronic grade sulfuric acid; thereby, an electronic grade can be provided. Sulfuric acid absorbs sulfur trioxide in the absorption tower (9) to produce electronic grade fuming sulfuric acid; further, the absorption tower may further have a sulfuric acid discharge pipe (not shown), and the sulfuric acid discharge pipe And an ultrapure water feed pipe (not shown) is connected to feed ultrapure water, wherein the ultrapure water can dilute the electronic grade fuming sulfuric acid discharged from the absorption tower into electronic grade sulfuric acid, and the sulfuric acid is out The subsequent stage of the feed pipe can be branched back to the absorption tower, so that the electronic grade sulfuric acid prepared by the ultrapure water dilution can be further shunted back to the suction. The tower is further absorbing sulfur trioxide in the absorption tower to continuously prepare electronic grade fuming sulfuric acid.
本發明將以下列實施例詳細加以說明，惟該等實施例僅為說明目的，而非用以限制本發明之範圍。The invention will be described in detail by the following examples, which are intended to be illustrative only and not to limit the scope of the invention.
取半導體業廢硫酸2 kg為原料，於廢硫酸進料管(3’)將廢硫酸饋入蒸餾塔(10)內進行減壓蒸餾，該廢硫酸含有硫酸62%、過氧化氫10%、水28%，於起始壓力為常壓750 mmHg的條件下，減壓至15 mmHg，先於反應溫度170℃之前將過氧化氫與約9成的水餾除，之後再於220℃下最終蒸餾得到98%工業級硫酸1240 g，過程所需時間約為24小時。接著，由廢硫酸進料管(3)將所得之98%工業級硫酸1 kg饋入第一反應槽(1)，且經由脫水劑進料管(4)將偏磷酸2.0 kg饋入第一反應槽(1)內，於反應槽溫度230℃於常壓下反應，該第一反應槽(1)所產出的三氧化硫，經由三氧化硫出料管(5)饋入吸收塔(9)中，於該吸收塔內藉由通入98%工業級硫酸約0.85 kg進行三氧化硫吸收，反應後得三氧化硫游離濃度15%的發煙硫酸約1.1 kg，而三氧化硫產率為約30%，其計算公式如下：
發煙硫酸重(kg)Fuming sulfuric acid weight (kg)
吸收塔工業級硫酸進料重(kg)Absorption tower industrial grade sulfuric acid feed weight (kg)
反應槽工業級硫酸進料重(kg)(上式中80/98中之數值分別表示硫酸分子量及三氧化硫分子量)Reaction tank industrial grade sulfuric acid feed weight (kg) (the values in 80/98 in the above formula represent the molecular weight of sulfuric acid and the molecular weight of sulfur trioxide, respectively)
半導體業廢硫酸之減壓蒸餾步驟如實施例1，由廢硫酸進料管(3)饋入98%工業級硫酸1 kg，且由脫水劑進料管(4)饋入偏磷酸3.9 kg於第一反應槽(1)內，反應溫度300℃於660 torr下反應，該第一反應槽(1)所產出的三氧化硫，經由三氧化硫出料管(5)饋入吸收塔(9)中，並透過硫酸進料管(11)饋入98%工業級硫酸約1.25 kg至吸收塔(9)中進行吸收，反應後得三氧化硫游離濃度26%的發煙硫酸1.84 kg，而三氧化硫產率以前述式計算為約74.3%。The vacuum distillation step of waste sulfuric acid in the semiconductor industry is as in Example 1. The waste sulfuric acid feed pipe (3) is fed with 98% of industrial grade sulfuric acid 1 kg, and the dehydrating agent feed pipe (4) is fed with metaphosphoric acid of 3.9 kg. In the first reaction tank (1), the reaction temperature is 300 ° C and reacted at 660 torr, and the sulfur trioxide produced by the first reaction tank (1) is fed into the absorption tower via the sulfur trioxide discharge pipe (5) ( 9), through the sulfuric acid feed pipe (11) fed 98% industrial grade sulfuric acid about 1.25 kg to the absorption tower (9) for absorption, the reaction obtained sulfur dioxide free concentration of 26% of fuming sulfuric acid 1.84 kg, The sulfur trioxide yield was calculated to be about 74.3% by the above formula.
半導體業廢壓硫酸之減蒸餾步驟如實施例1，由廢硫酸進料管(3)饋入98%工業級硫酸1 kg，且由脫水劑進料管(4)饋入偏磷酸2.9 kg於第一反應槽(1)內，反應溫度250℃於常壓下反應，該第一反應槽(1)所產出的三氧化硫，經由三氧化硫出料管(5)饋入吸收塔中，並將98%電子級硫酸1.28 kg經由第二硫酸進料管饋入該吸收塔(9)中進行吸收，製得22.5%電子級發煙硫酸1.8 kg，該吸收塔(9)之硫酸出料管與一超純水進料管連接，該超純水進料管饋入超純水150 g，而製得97%電子級硫酸約1.95 kg，所製得之電子級硫酸之規格經ICP-MS儀器進行金屬含量分析，其數據如下表1所示。三氧化硫產率為約64.6%，其計算公式如下：
電子級硫酸出料重(kg)Electronic grade sulfuric acid discharge weight (kg)
電子級硫酸進料重(kg)Electronic grade sulfuric acid feed weight (kg)
反應槽工業級硫酸進料重(kg)Reaction tank industrial grade sulfuric acid feed weight (kg)
硫酸含量(%)Sulfuric acid content (%)
半導體業廢硫酸之減壓蒸餾步驟如實施例1，由廢硫酸進料管(3)饋入98%工業級硫酸1 kg，且由脫水劑進料管(4)饋入偏磷酸7.8 kg於第一反應槽(1)內，反應溫度350℃於660 torr下反應，該第一反應槽(1)所產出的三氧化硫，經由三氧化硫出料管(5)饋入吸收塔(9)中，並將98%電子級硫酸1.52 kg經由第二硫酸進料管饋入該吸收塔(9)中進行吸收，製得26.7%電子級發煙硫酸2.26 kg，該吸收塔(9)之硫酸出料管與一超純水進料管連接，該超純水進料管饋入超純水240 g，而製得96%電子級硫酸約2.5 kg，而三氧化硫產率為約92.1%。所製得之電子級硫酸之規格經ICP-MS儀器進行金屬含量分析，其數據如下表1所示。The vacuum distillation step of waste sulfuric acid in the semiconductor industry is as in Example 1. The waste sulfuric acid feed pipe (3) is fed with 98% of industrial grade sulfuric acid 1 kg, and the dehydrating agent feed pipe (4) is fed with metaphosphoric acid of 7.8 kg. In the first reaction tank (1), the reaction temperature is 350 ° C at 660 torr, and the sulfur trioxide produced by the first reaction tank (1) is fed into the absorption tower via the sulfur trioxide discharge pipe (5) ( 9), and feeding 98% electronic grade sulfuric acid 1.52 kg into the absorption tower (9) via a second sulfuric acid feed pipe for absorption, and obtaining 26.7% electronic grade fuming sulfuric acid 2.26 kg, the absorption tower (9) The sulfuric acid discharge pipe is connected with an ultrapure water feed pipe, and the ultrapure water feed pipe feeds 240 g of ultrapure water to obtain 96% of electronic grade sulfuric acid of about 2.5 kg, and the sulfur trioxide yield is about 92.1%. The specifications of the obtained electronic grade sulfuric acid were analyzed by metal content analysis by an ICP-MS instrument, and the data are shown in Table 1 below.
依據上述實施例，可知利用本發明之方法，由於其係自廢硫酸中製備三氧化硫，而不必額外添加含硫物質，故而可達到資源再利用 的優點；且所使用之脫水劑係為液態，故可便於本發明之三氧化硫之製法工業化；再者，由於整體反應溫度較低，大幅降低習知三氧化硫之製程中因高溫所帶來的危險性，且可減少設備成本。此外，三氧化硫生成所產生的副產物磷酸可透過熱分解，使除水而生成液態之脫水劑，可重複用於製程中，達到製程方便、重複使用且降低成本之功效；又所得之產物三氧化硫，若收集固體容易因溫度升高而有氣爆的危險，且液態三氧化流與水接觸而形成爆炸性反應的可能，因此該所得的三氧化硫可進一步視需要經工業級硫酸或電子級吸收而產出發煙硫酸或電子級發煙硫酸以進行收集。According to the above embodiment, it can be seen that by using the method of the present invention, since sulfur trioxide is prepared from waste sulfuric acid without additional sulfur-containing substances, resource recycling can be achieved. The advantage is that the dehydrating agent used is in a liquid state, so that the method for producing sulfur trioxide according to the present invention can be facilitated; further, since the overall reaction temperature is low, the process of the conventional sulfur trioxide is greatly reduced due to the high temperature. The danger is coming and the cost of equipment can be reduced. In addition, the by-product phosphoric acid produced by the formation of sulfur trioxide can be thermally decomposed to form a liquid dehydrating agent in addition to water, which can be repeatedly used in the process to achieve the advantages of convenient process, repeated use and cost reduction; Sulfur trioxide, if the collected solids are prone to the risk of gas explosion due to the increase in temperature, and the liquid trioxide stream is in contact with water to form an explosive reaction, the resulting sulfur trioxide can be further subjected to industrial grade sulfuric acid or The electronic grade absorbs and produces sulphuric acid or electronic grade fuming sulfuric acid for collection.
1‧‧‧第一反應槽1‧‧‧First reaction tank
2‧‧‧第二反應槽2‧‧‧Second reaction tank
3‧‧‧廢硫酸進料管3‧‧‧Waste sulfuric acid feed pipe
3’‧‧‧廢硫酸進料管3'‧‧‧Waste sulfuric acid feed pipe
4‧‧‧脫水劑進料管4‧‧‧Dehydrator feed tube
5‧‧‧三氧化硫出料管5‧‧‧ sulfur trioxide discharge pipe
6‧‧‧第一反應槽槽底液出料管6‧‧‧First reaction tank bottom liquid discharge pipe
7‧‧‧第二反應槽出料管7‧‧‧Second reaction tank discharge pipe
8‧‧‧第二反應槽槽底液出料管8‧‧‧Second reaction tank bottom liquid discharge pipe
9‧‧‧吸收塔9‧‧‧ absorption tower
10‧‧‧蒸餾塔10‧‧‧Distillation tower
11‧‧‧硫酸進料管11‧‧‧ sulfuric acid feed tube
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| TW539642B (en) * | 1999-06-03 | 2003-07-01 | Rohm & Haas | Process for generating recoverable sulfur containing compounds from a spent acid stream |
| CN1986390A (en) * | 2006-12-26 | 2007-06-27 | 四川泸天化股份有限公司 | Process of purifying and recovering waste sulfuric acid containing organic impurity |
| US20080056982A1 (en) * | 2006-08-30 | 2008-03-06 | Danny Mislenkov | Process for recycling waste acid |
| CN101200288A (en) * | 2006-09-08 | 2008-06-18 | 催化剂蒸馏技术公司 | Low temperature process for regenerating spent sulfuric acid |
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| US20080056982A1 (en) * | 2006-08-30 | 2008-03-06 | Danny Mislenkov | Process for recycling waste acid |
| CN101200288A (en) * | 2006-09-08 | 2008-06-18 | 催化剂蒸馏技术公司 | Low temperature process for regenerating spent sulfuric acid |
| CN1986390A (en) * | 2006-12-26 | 2007-06-27 | 四川泸天化股份有限公司 | Process of purifying and recovering waste sulfuric acid containing organic impurity |
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