DE3910130C3 - Process for the preparation of concentrated solutions of sodium sulfite and sodium sulfate originating from flue gas desulfurization - Google Patents
Process for the preparation of concentrated solutions of sodium sulfite and sodium sulfate originating from flue gas desulfurizationInfo
- Publication number
- DE3910130C3 DE3910130C3 DE3910130A DE3910130A DE3910130C3 DE 3910130 C3 DE3910130 C3 DE 3910130C3 DE 3910130 A DE3910130 A DE 3910130A DE 3910130 A DE3910130 A DE 3910130A DE 3910130 C3 DE3910130 C3 DE 3910130C3
- Authority
- DE
- Germany
- Prior art keywords
- flue gas
- gas desulfurization
- gypsum
- sodium
- sodium sulfite
- 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.)
- Expired - Fee Related
Links
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 title claims description 19
- 239000003546 flue gas Substances 0.000 title claims description 10
- 235000010265 sodium sulphite Nutrition 0.000 title claims description 10
- 238000000034 method Methods 0.000 title claims description 9
- 235000011152 sodium sulphate Nutrition 0.000 title claims description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 title claims description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 title claims description 7
- 238000006477 desulfuration reaction Methods 0.000 title claims description 6
- 230000023556 desulfurization Effects 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000010440 gypsum Substances 0.000 claims description 7
- 229910052602 gypsum Inorganic materials 0.000 claims description 7
- 239000010865 sewage Substances 0.000 claims description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 5
- 239000004571 lime Substances 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 5
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims description 5
- 239000006096 absorbing agent Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000002485 combustion reaction Methods 0.000 claims description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims 2
- 235000019738 Limestone Nutrition 0.000 claims 2
- 239000002826 coolant Substances 0.000 claims 2
- 239000006028 limestone Substances 0.000 claims 2
- 239000010801 sewage sludge Substances 0.000 claims 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims 1
- 239000007832 Na2SO4 Substances 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 229910000019 calcium carbonate Inorganic materials 0.000 claims 1
- 235000010216 calcium carbonate Nutrition 0.000 claims 1
- 239000011593 sulfur Substances 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 5
- 239000001110 calcium chloride Substances 0.000 description 5
- 229910001628 calcium chloride Inorganic materials 0.000 description 5
- 235000011148 calcium chloride Nutrition 0.000 description 5
- 239000011734 sodium Substances 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
- C01F11/464—Sulfates of Ca from gases containing sulfur oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
- C01D3/06—Preparation by working up brines; seawater or spent lyes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Treating Waste Gases (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Die Erfindung betrifft ein Verfahren zum Aufbereiten von aus einer Rauchgasentschwefelung stammenden konzentrierten Lösungen von Natriumsulfit und Natriumsulfat (Produktlauge).The invention relates to a method for processing from a flue gas desulfurization concentrated Solutions of sodium sulfite and sodium sulfate (Product lye).
Aufgrund der in der Bundesrepublik Deutschland geltenden Großfeuerungsanlagen-Verordnung müssen die Rauchgase aus Kraftwerks-Feuerungsanlagen entschwefelt werden. Zu 87% wird dabei das Kalkwaschverfahren und zu 13% werden Sonderverfahren angewendet. Zu den Sonderverfahren gehört u. a. das Wellmann-Lord-Verfahren, bei dem die Rauchgase mit einer Natriumsulfitlösung gewaschen werden. Die entstehende Lauge wird erhitzt und dabei wird SO₂ ausgetrieben, aber auch in einer Nebenreaktion Natriumsulfit oxidiert. Das Aufbereiten der beim Rauchgasentschwefeln nach dem Wellmann-Lord-Verfahren oder anderen Rauchgaswäschen auf Natriumsalzbasis in unerwartet großer Menge anfallenden Natriumsulfit und -sulfat haltigen Lauge bereitete große Probleme. Ein Ableiten war ebenso wenig erlaubt wie ein Deponieren. Auch war ein unter wirtschaftlichen Aspekten gangbarer Weg für die Aufbereitung dieser Produktlauge nicht in Sicht.Due to the valid in the Federal Republic of Germany Large combustion plant ordinance must remove the flue gases Power plant combustion plants are desulfurized. 87% will be the lime washing process and 13% Special procedures applied. One of the special procedures u. a. the Wellmann-Lord process, in which the flue gases are be washed with a sodium sulfite solution. The emerging Lye is heated and SO₂ is expelled, but also oxidized in a side reaction sodium sulfite. The Processing of the flue gas desulfurization after Wellmann-Lord process or other flue gas washers Sodium salt base in an unexpectedly large amount Lye containing sodium sulfite and sulfate prepared large Problems. Deriving was just as little allowed as one Deposit. Also one was from an economic point of view not a viable route for the treatment of this product lye in sight.
Der Erfindung liegt nun die Aufgabe zugrunde, eine technisch durchführbare Konzeption für die Aufbereitung von Produktlauge zu schaffen, die auch unter wirtschaftlichen Gesichtspunkten vertretbar ist.The invention is based on the object, a technical feasible conception for the preparation of To create product lye that is also economical Point of view is justifiable.
Zur Lösung dieser Aufgabe werden erfindungsgemäß die Maßnahmen des Patenanspruchs vorgeschlagen.To solve this task according to the invention, the measures of the patent claim suggested.
Das erfindungsgemäße Verfahren löst einmal die gestellte Aufgabe, denn es bietet eine Möglichkeit, die Produktlauge in ein vorhandenes System einzuspeisen und darin aufzubereiten. Es entfallen daher besondere Anlagen oder Einrichtungen für die Aufbereitung der Produktlauge, und es werden auch keine Zusatzstoffe benötigt, wodurch die Verfahrensweise außerordentlich wirtschaftlich durchführbar ist. Als zusätzlicher Vorteil ergibt sich eine Verminderung der sonst für die Neutralisation der Salzsäure in der Kläranlage benötigten Menge an Löschkalk. Eine zusätzliche Sulfatbelastung des abgeleiteten REA-Wassers tritt nicht auf, weil das im Rohabwasser zusätzlich enthaltene Sulfat als Gips gefällt wird. Auch der CSB-Wert, verursacht durch organische Wasserinhaltsstoffe, wird nur geringfügig und innerhalb der zulässigen Grenzwerte verändert. Sulfit und Thiosulfat waren im Abwasser nicht nachweisbar.The method according to the invention solves the problem Task, because it offers a way of product lye feed into and into an existing system prepare. There are therefore no special systems or Equipment for the treatment of the product liquor, and it no additives are required, which means that Procedure extremely economically feasible is. A further advantage is a reduction who is otherwise responsible for the neutralization of hydrochloric acid in the Sewage treatment plant required amount of hydrated lime. An additional Sulphate pollution in the derived REA water does not occur because the sulfate additionally contained in the raw sewage when plaster is felled. The COD value caused by organic water constituents, is only marginally and changed within the permissible limit values. Sulfite and Thiosulfate was not detectable in the waste water.
Durch den Eintrag der Produktlauge in den Kühler wird zwar die Sulfatkonzentration und die Natriumkonzentration gesteigert, jedoch konnte ein Einfluß auf den Absorber hierdurch nicht festgestellt werden. Dagegen haben die Natriumsalze das Verschmutzungsverhalten der Tropfenabscheider im Kühler wegen der Erhöhung der Gipslöslichkeit durch Natriumchlorid positiv beeinflußt.By entering the product lye in the cooler the sulfate concentration and the sodium concentration increased, but could have an impact on the absorber cannot be determined by this. In contrast, they have Sodium salts the pollution behavior of the Droplet separator in the cooler because of the increase in Gypsum solubility positively influenced by sodium chloride.
Fig. 1 zeigt schematisch den Stofffluß innerhalb der REA, in welcher die Produktlauge umgesetzt wird. Fig. 1 shows schematically the material flow within the REA, in which the product liquor is implemented.
Anhand des folgenden Beispiels wird die Erfindung näher erläutert.The invention is illustrated by the following example explained.
1 m3/h Produktlauge, bestehend aus einer wäßrigen Lösung von Natriumsulfat (Na2SO4), Natriumsulfit (Na2SO3), Natriumthiosulfat (Na2S2O3) und komplexgebundenem EDTA wurden mit 160 kg/h HCl aus dem Rauchgas eines Kraftwerks und 36 t/h Wasser dem Vorwäscher (Kühler) einer REA zugeführt. Durch die Zugabe der Produktlauge zu dem sauren Kühlerwasser (pH kleiner als 1) erfolgen mit dem Natriumsulfit und Natriumthiosulfat folgende Umsetzungen:1 m 3 / h of product liquor, consisting of an aqueous solution of sodium sulfate (Na 2 SO 4 ), sodium sulfite (Na 2 SO 3 ), sodium thiosulfate (Na 2 S 2 O 3 ) and complex-bound EDTA, were extracted from the Flue gas from a power plant and 36 t / h of water fed to the pre-washer (cooler) of a FGD By adding the product liquor to the acidic cooler water (pH less than 1), the following reactions take place with the sodium sulfite and sodium thiosulfate:
2 HCl + Na₂SO₃ → 2 NaCl + H₂O + SO₂ (1)
2 HCl + Na₂S₂O₃ → 2 NaCl + S + H₂O + SO₂ (2)2 HCl + Na₂SO₃ → 2 NaCl + H₂O + SO₂ (1)
2 HCl + Na₂S₂O₃ → 2 NaCl + S + H₂O + SO₂ (2)
Die im Kühler vorhandene Salzsäure wird somit durch Sulfit und Thiosulfat teilweise neutralisiert und das Säureäquivalent als SO2 freigesetzt. Die Zugabe von Produktlauge ist so zu bemessen, daß ein Überschuß an Säure zurückbleibt. Auf diese Weise ist sichergestellt, daß Sulfit und Thiosulfat im Kühler quantitativ umgesetzt werden. Das entstehende SO2 in einer Menge von 60 kg/h wird im nachgeschalteten Absorber ausgewaschen und mit 29 t/h Wasser und 100 kg/h Kalk (CaCO3) zu Gips verarbeitet.The hydrochloric acid present in the cooler is thus partially neutralized by sulfite and thiosulfate and the acid equivalent is released as SO 2 . The addition of product lye should be such that an excess of acid remains. This ensures that sulfite and thiosulfate are converted quantitatively in the cooler. The resulting SO 2 in an amount of 60 kg / h is washed out in the downstream absorber and processed into gypsum with 29 t / h water and 100 kg / h lime (CaCO 3 ).
Die in der Produktlauge enthaltenen Schwermetalle liegen in nur unbedeutender Konzentration vor, so daß die Schwermetallbilanz nicht signifikant verändert wird.The heavy metals contained in the product lye lie in insignificant concentration, so that the Heavy metal balance is not significantly changed.
Das in den Vorwäschern mit der Produktlauge eingebrachte Natriumsulfat verläßt das System unverändert mit der Abwasserabschlemmung zur Kläranlage.That introduced in the prewashers with the product lye Sodium sulfate leaves the system unchanged with the Wastewater drainage to the sewage treatment plant.
Durch die Neutralisation mit Löschkalk (Ca(OH)2) wird aus überschüssiger Salzsäure nach der BildungsgleichungThe neutralization with hydrated lime (Ca (OH) 2 ) turns excess hydrochloric acid into the equation of formation
Ca(OH)₂ + 2 HCl → CaCl₂ + 2 H₂O (3)Ca (OH) ₂ + 2 HCl → CaCl₂ + 2 H₂O (3)
Calciumchlorid gebildet. In einer doppelten Umsetzung fällt aus Calciumchlorid mit Natriumsulfat Gips aus:Calcium chloride formed. In a double implementation from calcium chloride with sodium sulfate gypsum from:
Die Reaktion ist vollständig, wenn ein Überschuß an Calciumchlorid in einer Menge von 200 kg/h gegenüber Natriumsulfat (90 kg/h) eingehalten wird.The reaction is complete when there is an excess Calcium chloride in an amount of 200 kg / h compared Sodium sulfate (90 kg / h) is observed.
Anstelle des sonst üblicherweise abgeleiteten Calciumchlorids wird nun eine äquivalente Menge Natriumchlorid an den Vorfluter abgegeben.Instead of what is usually derived Calcium chloride will now be an equivalent amount Sodium chloride released to the receiving water.
Die Abwassermenge der REA wird nicht verändert, weil durch die Produktlauge ein Teil des Zusatzwasserbedarfs des Kühlers gedeckt wird. Dagegen kommt wie gesagt eine Einsparung beim Kalkbedarf in der Kläranlage zum Tragen.The amount of waste water from the REA is not changed because the product lye is part of the make-up water requirement of the Cooler is covered. On the other hand, as I said, there is one Savings in lime requirements in the sewage treatment plant to bear.
Claims (1)
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3910130A DE3910130C3 (en) | 1989-03-29 | 1989-03-29 | Process for the preparation of concentrated solutions of sodium sulfite and sodium sulfate originating from flue gas desulfurization |
ES9001119A ES2019824A6 (en) | 1989-03-29 | 1990-03-28 | Process for preparing a concentrated solution of sodium sulphite and sulphate originating, in particular, from flue gas desulphurisation |
IT47796A IT1239442B (en) | 1989-03-29 | 1990-03-28 | PROCEDURE FOR THE PREPARATION OF A CONCENTRATED SOLUTION OF SODIUM SULPHATE AND SODIUM SULPHATE COMING FROM THE DESOLFORATION OF COMBUSTION GAS. |
CS901548A CZ283577B6 (en) | 1989-03-29 | 1990-03-29 | Process of treating concentrated solution of sodium sulfite, sulfate and thiosulfate |
SK1548-90A SK279928B6 (en) | 1989-03-29 | 1990-03-29 | Method for processing a concentrated solution of sodium sulphite, sodium sulphate and sodium thiosulphate |
SU904743537A RU2049063C1 (en) | 1989-03-29 | 1990-03-29 | Process for treating concentrated sulfite-sulfate solution into gypsum |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3910130A DE3910130C3 (en) | 1989-03-29 | 1989-03-29 | Process for the preparation of concentrated solutions of sodium sulfite and sodium sulfate originating from flue gas desulfurization |
Publications (3)
Publication Number | Publication Date |
---|---|
DE3910130A1 DE3910130A1 (en) | 1990-10-04 |
DE3910130C2 DE3910130C2 (en) | 1991-01-03 |
DE3910130C3 true DE3910130C3 (en) | 1995-02-09 |
Family
ID=6377373
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE3910130A Expired - Fee Related DE3910130C3 (en) | 1989-03-29 | 1989-03-29 | Process for the preparation of concentrated solutions of sodium sulfite and sodium sulfate originating from flue gas desulfurization |
Country Status (6)
Country | Link |
---|---|
CZ (1) | CZ283577B6 (en) |
DE (1) | DE3910130C3 (en) |
ES (1) | ES2019824A6 (en) |
IT (1) | IT1239442B (en) |
RU (1) | RU2049063C1 (en) |
SK (1) | SK279928B6 (en) |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3607357C1 (en) * | 1986-03-06 | 1987-05-07 | Babcock Anlagen Ag | Process for cleaning flue gases containing SO2 |
-
1989
- 1989-03-29 DE DE3910130A patent/DE3910130C3/en not_active Expired - Fee Related
-
1990
- 1990-03-28 ES ES9001119A patent/ES2019824A6/en not_active Expired - Lifetime
- 1990-03-28 IT IT47796A patent/IT1239442B/en active IP Right Grant
- 1990-03-29 RU SU904743537A patent/RU2049063C1/en active
- 1990-03-29 CZ CS901548A patent/CZ283577B6/en unknown
- 1990-03-29 SK SK1548-90A patent/SK279928B6/en unknown
Also Published As
Publication number | Publication date |
---|---|
CZ154890A3 (en) | 1998-02-18 |
ES2019824A6 (en) | 1991-07-01 |
SK154890A3 (en) | 1999-05-07 |
DE3910130C2 (en) | 1991-01-03 |
IT9047796A0 (en) | 1990-03-28 |
SK279928B6 (en) | 1999-05-07 |
IT1239442B (en) | 1993-11-02 |
DE3910130A1 (en) | 1990-10-04 |
CZ283577B6 (en) | 1998-05-13 |
RU2049063C1 (en) | 1995-11-27 |
IT9047796A1 (en) | 1991-09-28 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
OP8 | Request for examination as to paragraph 44 patent law | ||
D2 | Grant after examination | ||
8363 | Opposition against the patent | ||
8366 | Restricted maintained after opposition proceedings | ||
8305 | Restricted maintenance of patent after opposition | ||
D4 | Patent maintained restricted | ||
8327 | Change in the person/name/address of the patent owner |
Owner name: PREUSSENELEKTRA KRAFTWERKE AG, PEK, 45896 GELSENKI |
|
8327 | Change in the person/name/address of the patent owner |
Owner name: E.ON ENGINEERING GMBH, 45896 GELSENKIRCHEN, DE |
|
8339 | Ceased/non-payment of the annual fee |