CN1071784C - 带有腐蚀抑制剂的吸收式冷冻系统工作流质 - Google Patents
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- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
- C23F11/187—Mixtures of inorganic inhibitors
- C23F11/188—Mixtures of inorganic inhibitors containing phosphates
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
- C09K5/047—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for absorption-type refrigeration systems
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
- C23F11/187—Mixtures of inorganic inhibitors
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
一种吸收式冷冻系统用的抑制腐蚀的工作流质和制备这种流质的方法。该流质是锂的卤盐或氨的水溶液，添加了含有钼酸盐、硼酸盐、和(在较佳实施例中)硅酸盐的水溶性化合物。揭示了最终钼离子、硼离子、和硅离子的较佳浓度。还加入了含有氢氧化物的水溶性化合物，以产生碱性规度。在较佳的制备方法中，添加化合物是以水溶液形式加入至工作流质中。
Description
本发明粗略地说涉及吸收式冷冻系统，具体地说涉及用于该种系统的抑制腐蚀的工作流质和制备这种流质的方法。所述流质含有腐蚀抑制剂，可减少系统中与系统工作流质接触的金属的腐蚀。
有许多不同的冷冻剂和吸收剂组可用于吸收式冷冻系统。其中的一组是水和一种锂的卤盐，如溴化锂、氯化锂或碘化锂，它们混合在一起构成浓的锂盐水溶液。另外一组是水和氨。
铁和铁合金(如钢)以及铜和铜合金是吸收式冷冻系统中所用的典型结构材料。这些材料的腐蚀会引起困难。不仅因为金属的损失，而且因为亚铁金属的氧化会产生气态的氢。如果不清除掉，氢气会干扰系统的正常工作。在使用锂的卤盐的系统中，腐蚀更是特别令人关切。而不论某一特定系统所用的是哪种冷冻剂/吸收剂组，金属腐蚀率总是随系统温度上升而增加。
现有技术知道，在吸收式冷冻系统的冷冻剂/吸收剂溶液中加入一种铬盐，例如铬酸锂，可有效地减少金属腐蚀。铬酸盐化合物的存在，有助于在与吸收剂接触的系统表面形成氧化铁和氧化铬保护层。随着铁的氧化减少，不能凝聚的氢的产生也相应地减少。但是，人们担心铬所引起的健康问题。至少有一个政府机构，美国环境保护局，已明确指出铬是致癌物，并禁止在开放于大气的系统中存在铬化合物。到写作本文时，还没有限制在封闭系统中使用铬化合物，但可能在不久的将来就会限制。吸收式冷冻系统当然是封闭系统，但是在取样时，在制造过程中，和搬运、充液过程中溢出时，都会使系统中的相当数量的工作流质暴露于大气中。而且，在系统使用寿命结束时，系统的负荷将必然要求处理工作流质，包括处理其中所含的铬化合物。
现在需要的是一种用于吸收式冷冻系统的工作流质，它含有能有效地减少系统中金属部件腐蚀的抑制剂，同时不存在那些含有铬化合物的抑制剂对环境和健康的不良影响。该流质应可适用于各种不同类型的系统，而且即使在三重效果吸收系统(triple effectabsorption system)和燃烧天然气或丙烷的系统中所承受的极高温度下，也能有效地抑制腐蚀。
本发明是一种锂的卤盐或氨的不含铬的水溶液，用作吸收式冷冻系统的工作流质。除了锂盐或氨以外，该溶液还包括含有钼酸盐的化合物、含有硼酸盐的化合物、以及(在较佳实施例中)含有硅酸盐的化合物，使工作流质中存在钼、硼、和硅的离子。在溶液中还加有充分数量的含有氢氧化物的化合物，使它呈较强的碱性。所加的组元起着有效的腐蚀抑制剂的作用。该流体的腐蚀抑制性能优于现有技术所用的铬酸锂抑制剂。
本发明提供一种吸收式冷冻系统用的工作流质，它包括至少一种选自溴化锂、氯化锂和碘化锂化合物的水溶液，所述溶液还含有：
足以使所述溶液中钼浓度为10-500ppm的钼酸盐；
足以使所述溶液中硼浓度为1-10,000ppm的硼酸盐；和
足以使所述溶液中的硅浓度为1-20ppm的硅酸盐。
在锂盐或氨的水溶液中加入钼、硼、和(在较佳实施例中)硅的卤盐或氨盐，得到一工作流质。还加入钠、锂、钾或铵的氢氧化物，以获得所需的碱性当量浓度。所加的化合物最好以水溶液的形式加入。
对本发明工作流质的一个实施例的腐蚀抑制性能，在实验室条件下用钢和铜样品以及在运行的冷冻系统中都作了测试。测试结果表明，该流质的抗腐蚀性优于铬酸盐抑制剂以及其它抑制剂和抑制剂混合物。
本发明的工作流质是一种卤盐或氨的水溶液。流质中还含有抑制腐蚀的钼和硼离子的混合物。在一个实施例中，该混合物还含有硅离子。在流质中也加入了含有氢氧化物的化合物，以加入羟离子，并使溶液具有碱性规度。所存在的钼、硼、和硅离子，是通过加入分别含有钼酸盐、硼酸盐、和硅酸盐的化合物而得到的。
特定的吸收式冷冻系统一般以溴化锂、氯化锂、碘化锂或氨的水溶液作为工作流质。系统的工作流质也可以是锂的两种或更多种卤盐的水溶液。含有钼酸盐、硼酸盐、和硅酸盐的腐蚀抑制化合物最好是流质基本组元的相似盐类。因此，工作流质为水和溴化锂时，添加的化合物最好是钼酸锂、硼酸锂、和硅酸锂。规度也最好通过添加氢氧化锂来调节。工作流质为水和氨时，添加的化合物最好是钼酸铵、锂或钠，硼酸铵、锂或钠，和硅酸铵、锂或钠，规度最好是通过加入氢氧化铵、锂或钠来调节。但是，添加钼酸钾、硼酸钾、和硅酸钾，并用氢氧化钾来调节规度(normality，即当量浓度)，也得到满意的结果。
本发明的工作流质可用混合和溶解技术制备。例如可通过制备溴化锂的水溶液来制得抑制腐蚀的溴化锂工作流质。然后加入钼酸锂、硼酸锂、和(在较佳实施例中)硅酸锂以及氢氧化锂。添加化合物本身最好以水溶液形式加入到冷冻剂/吸收剂溶液中，而不要试图将这些化合物直接溶解在冷冻剂/吸收剂溶液中。
对按照本发明制备的溴化锂工作流质在实验室条件下和在运行的冷冻系统中都作了测试。一种流质中溴化锂基本水溶液含有55％重量溴化锂，即0.06N溶液。其它添加剂的浓度是150ppm重量的钼，190ppm的硼，和10ppm的硅。也测试了具有相似特征但不加硅化合物的流质。
测试结果表明，本发明的工作流质(含硅或不含硅的)与含铬的工作流质相比，其腐蚀抑制性能更为优良。实际腐蚀率随温度条件，金属类型，以及金属是暴露于汽相流质、液相流质、或暴露于该两相的流质等情况而变。但是，平均地说，使用本发明的工作流质时，铁和铜的腐蚀率约为使用不含腐蚀抑制剂的工作流质时的百分之一，而约为使用含有铬抑制剂的工作流质时的十分之一。加入含硅化合物，与其抑制剂混合物中不含硅的工作流质相比，性能仅略有提高。
根据测试数据，我们认为工作流质的规度为0.03-0.2，钼的浓度为10-500ppm，较好120-180ppm，硼的浓度为1-10,000ppm，较好160-220ppm，硅的浓度为1-20ppm时，将得到类似的测试结果。而且，相对低浓度的抑制剂添加物，从10ppm钼和1ppm硼起，就应对抑制腐蚀有作用。
测试表明，加入2-7基己醇等其它添加剂，不会影响本发明的工作流质的腐蚀抑制能力。本发明的工作流质在储存一段时间后会变得稍为混浊。混浊对其腐蚀抑制性能并无影响。本发明的工作流质也防止了被测试系统中的钢质部件镀上铜。在流质中不含钙杂质(最多1ppm)是非常重要的。
当工作流质装入系统以后，抑制剂混合物中的某些组分会随着时间而消耗，当系统在运行时，消耗率会增大。因此要把组分化合物的浓度提高到比所需的大，以顾及消耗。顾及消耗后，可能会要求钼的浓度高达500ppm，硼的浓度高达1％(10000ppm)，硅的浓度高达100ppm。
注意以上添加剂的浓度是对具有规定浓度的卤盐(一种或多种)或氨的工作流质而言的，例如对54-56％重量的溴化锂水溶液和10％重量的氨水溶液而言的。
Claims (4)
1．一种吸收式冷冻系统用的工作流质，它包括至少一种选自溴化锂、氯化锂和碘化锂化合物的水溶液，所述溶液还含有：
使所述溶液中钼浓度为10-500ppm的钼酸盐；
使所述溶液中硼浓度为1-10,000ppm的硼酸盐；和
使所述溶液中的硅浓度为1-20ppm的硅酸盐。
2．如权利要求1所述的吸收式冷冻系统用的工作流质，它包括至少一种选自溴化锂、氯化锂和碘化锂化合物的水溶液，所述溶液还含有：
使所述溶液中钼浓度为120-180ppm的钼酸盐；
使所述溶液中硼浓度为160-220ppm的硼酸盐；和
使所述溶液中的硅浓度为1-20ppm的硅酸盐。
3．如权利要求1或2所述的工作流质，其特征在于所述溶液还含有氢氧化物，以便形成碱性当量浓度。
4．如权利要求3所述的工作流质，其特征在于所述溶液的当量浓度为0.03-0.2。
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| US08/435930 | 1995-05-05 | ||
| US08/435,930 US5547600A (en) | 1995-05-05 | 1995-05-05 | Absorption refrigeration system working fluid with molybdate, borate, silicate inhibitor blend |
| US08/435,930 | 1995-05-05 |
Publications (2)
| Publication Number | Publication Date |
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| CN1183452A CN1183452A (zh) | 1998-06-03 |
| CN1071784C true CN1071784C (zh) | 2001-09-26 |
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| US (1) | US5547600A (zh) |
| EP (1) | EP0741179B1 (zh) |
| JP (1) | JP2686062B2 (zh) |
| KR (1) | KR100249879B1 (zh) |
| CN (1) | CN1071784C (zh) |
| BR (1) | BR9602129A (zh) |
| CA (1) | CA2174184C (zh) |
| CZ (1) | CZ289951B6 (zh) |
| DE (1) | DE69609011T2 (zh) |
| ES (1) | ES2148713T3 (zh) |
| RU (1) | RU2119936C1 (zh) |
| SI (1) | SI0741179T1 (zh) |
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| US6024892A (en) * | 1997-10-06 | 2000-02-15 | Fmc Corporation | Anticorrosion and pH stable alkali metal halide solutions for air dehumidification |
| US6177025B1 (en) | 1998-11-17 | 2001-01-23 | University Of Utah | Absorption heat pumps having improved efficiency using a crystallization-inhibiting additive |
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| US6203718B1 (en) * | 1999-08-30 | 2001-03-20 | Donald C. Erickson | Aqueous ammonia corrosion inhibitor |
| US6758988B1 (en) | 1999-09-07 | 2004-07-06 | Fmc Corporation | Corrosion inhibiting solutions for absorption systems |
| EP1352942A1 (en) * | 1999-09-07 | 2003-10-15 | Fmc Corporation | Corrosion inhibiting solutions for absorption systems |
| DE60008393T2 (de) * | 1999-09-07 | 2004-12-23 | Fmc Corp. | Korrosionsinhibierende lösungen für absorptionssysteme |
| WO2001029285A2 (en) * | 1999-10-19 | 2001-04-26 | Advanced Mechanical Technology, Inc. | Corrosion protection of steel in ammonia/water heat pumps |
| US6620341B1 (en) | 1999-12-23 | 2003-09-16 | Fmc Corporation | Corrosion inhibitors for use in oil and gas wells and similar applications |
| US6723258B1 (en) | 2000-06-30 | 2004-04-20 | Bulk Chemicals, Inc. | Method and composition for minimizing rust formation and improving paint adhesion of metal surfaces |
| DE10063951A1 (de) * | 2000-12-20 | 2002-06-27 | Basf Ag | Kühlmittel für Kühlsysteme in Brennstoffzellenantrieben |
| ITMI20012176A1 (it) | 2001-10-18 | 2003-04-18 | Robur Spa | Inibitore di corrosione per sistemi ad assorbimento ad acqua ed ammoniaca |
| GB0719848D0 (en) * | 2007-10-11 | 2007-11-21 | Reckitt Benckiser Uk Ltd | Aerosol compositions |
| RU2455585C2 (ru) * | 2010-04-05 | 2012-07-10 | Государственное образовательное учреждение высшего профессионального образования Санкт-Петербургский государственный университет низкотемпературных и пищевых технологий | Рабочее тело для абсорбционных холодильных машин и абсорбционных термотрансформаторов |
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-
1995
- 1995-05-05 US US08/435,930 patent/US5547600A/en not_active Expired - Lifetime
-
1996
- 1996-04-15 CA CA002174184A patent/CA2174184C/en not_active Expired - Fee Related
- 1996-04-25 EP EP96630024A patent/EP0741179B1/en not_active Expired - Lifetime
- 1996-04-25 ES ES96630024T patent/ES2148713T3/es not_active Expired - Lifetime
- 1996-04-25 DE DE69609011T patent/DE69609011T2/de not_active Expired - Lifetime
- 1996-04-25 SI SI9630190T patent/SI0741179T1/xx unknown
- 1996-04-30 CZ CZ19961252A patent/CZ289951B6/cs not_active IP Right Cessation
- 1996-04-30 RU RU96108967A patent/RU2119936C1/ru not_active IP Right Cessation
- 1996-05-02 BR BR9602129A patent/BR9602129A/pt not_active IP Right Cessation
- 1996-05-03 CN CN96106290A patent/CN1071784C/zh not_active Expired - Fee Related
- 1996-05-04 KR KR1019960014589A patent/KR100249879B1/ko not_active Expired - Fee Related
- 1996-05-07 JP JP8112350A patent/JP2686062B2/ja not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1183452A (zh) | 1998-06-03 |
| JPH08313099A (ja) | 1996-11-29 |
| CA2174184C (en) | 1999-12-07 |
| CZ125296A3 (en) | 1996-11-13 |
| EP0741179B1 (en) | 2000-06-28 |
| SI0741179T1 (en) | 2000-10-31 |
| DE69609011T2 (de) | 2000-11-16 |
| EP0741179A1 (en) | 1996-11-06 |
| BR9602129A (pt) | 1998-06-30 |
| US5547600A (en) | 1996-08-20 |
| RU2119936C1 (ru) | 1998-10-10 |
| DE69609011D1 (de) | 2000-08-03 |
| ES2148713T3 (es) | 2000-10-16 |
| KR100249879B1 (ko) | 2000-04-01 |
| KR960041423A (ko) | 1996-12-19 |
| JP2686062B2 (ja) | 1997-12-08 |
| CA2174184A1 (en) | 1996-11-06 |
| CZ289951B6 (cs) | 2002-05-15 |
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