JPH04191345A - Acid resistant material - Google Patents
Acid resistant materialInfo
- Publication number
- JPH04191345A JPH04191345A JP32075190A JP32075190A JPH04191345A JP H04191345 A JPH04191345 A JP H04191345A JP 32075190 A JP32075190 A JP 32075190A JP 32075190 A JP32075190 A JP 32075190A JP H04191345 A JPH04191345 A JP H04191345A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- resistant material
- corrosion resistance
- weight
- present
- 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.)
- Pending
Links
- 239000004063 acid-resistant material Substances 0.000 title claims abstract description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 16
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 15
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 29
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 14
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 14
- 239000011733 molybdenum Substances 0.000 claims description 13
- 239000011651 chromium Substances 0.000 claims description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 11
- 229910052804 chromium Inorganic materials 0.000 claims description 11
- 239000000463 material Substances 0.000 abstract description 29
- 230000007797 corrosion Effects 0.000 abstract description 23
- 238000005260 corrosion Methods 0.000 abstract description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 20
- 239000002253 acid Substances 0.000 abstract description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 abstract description 10
- 229910000599 Cr alloy Inorganic materials 0.000 abstract description 7
- 150000007513 acids Chemical class 0.000 abstract description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 6
- -1 platinum group metals Chemical class 0.000 abstract description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 abstract description 5
- 235000019253 formic acid Nutrition 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 4
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 4
- 238000004821 distillation Methods 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- 150000007522 mineralic acids Chemical class 0.000 abstract description 3
- 150000007524 organic acids Chemical class 0.000 abstract description 3
- 235000005985 organic acids Nutrition 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 150000004820 halides Chemical class 0.000 abstract description 2
- 239000011780 sodium chloride Substances 0.000 abstract description 2
- 238000010306 acid treatment Methods 0.000 abstract 1
- 239000004035 construction material Substances 0.000 abstract 1
- 241000196324 Embryophyta Species 0.000 description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 150000001844 chromium Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000788 chromium alloy Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000015429 Mirabilis expansa Nutrition 0.000 description 1
- 244000294411 Mirabilis expansa Species 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 235000013536 miso Nutrition 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、各種酸水溶液に対して用いられる各種の機器
の材料として適した耐酸材料に関するものである。詳細
には、モリブデンを２から３０重量％含有し、かつルテ
ニウム、プラチナ、パラジウムからなる元素のうち少な
くとも１種以上の金属を合計で０．１から１０重量％含
有し残部が実質的にクロムからなる耐酸材料に関するも
のである。そして、これらの機器としては、化学プラン
トあるいは酸処理プラントにおける蒸留搭、反応器、熱
交換器、配管及びタンクなどがあり、これらの母材ある
いは、クラッド、ライニング材として特に有効な耐酸材
料を提供するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an acid-resistant material suitable as a material for various equipment used for various acid aqueous solutions. Specifically, it contains 2 to 30% by weight of molybdenum, a total of 0.1 to 10% by weight of at least one metal selected from the elements consisting of ruthenium, platinum, and palladium, and the remainder is substantially composed of chromium. The invention relates to acid-resistant materials. These devices include distillation columns, reactors, heat exchangers, piping, and tanks in chemical plants or acid processing plants, and we provide acid-resistant materials that are particularly effective as base materials, cladding, and lining materials for these devices. It is something to do.
［従来の技術及びその問題点］
従来、硫酸、硝酸、リン酸、ギ酸、酢酸、塩酸、あるい
は各種混酸等の材料としては、ステンレス鋼、高Ｃｒ合
金、Ｚｒｓ Ｎｂ、Ｔａ５Ｔｉあるいはゴムライニング
、樹脂ライニング、グラスライニング、テフロンライニ
ングが用いられている。[Prior art and its problems] Conventionally, materials for sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, hydrochloric acid, or various mixed acids include stainless steel, high Cr alloy, Zrs Nb, Ta5Ti, rubber lining, and resin lining. , glass lining, and Teflon lining are used.
一般に硫酸、リン酸等の還元性無機酸溶液中では、５Ｕ
Ｓ３０４をはじめとするＦｅ−Ｃｒ−Ｎｉ系の合金が用
いられている。しかし、これらの材料は加工性は良好で
あるが、高温、高濃度の酸溶液中での耐食性に乏しく、
塩酸、フッ酸等が混入すると激しい腐食を受ける。この
ため使用環境が著しく制限されている。Ｔｉ・又はＴｉ
合金は硝酸を初めとする種々の酸溶液中で充分な耐食性
を有しているか、塩酸、フッ酸等の・＼ロケン化物を含
んだ酸、あるいはリン酸、硫酸等の還元性の酸溶液中に
おいての耐食性に乏しく、このため使用環境か著しく制
限されている。金属材料の適応の困難な部分あるいは環
境では、ゴムライニング、樹脂ライニングか用いられる
か、高温環境に弱く、伝熱か悪いという欠点を有してい
る。Ｚｒ、Ｎｂ、Ｔａは幅広い組成の酸溶液中において
充分な耐食性を有しているが、非常に高価な材料である
ため、幅広く大型の機器に適応することは困難である。Generally, in reducing inorganic acid solutions such as sulfuric acid and phosphoric acid, 5U
Fe-Cr-Ni alloys such as S304 are used. However, although these materials have good processability, they have poor corrosion resistance at high temperatures and in highly concentrated acid solutions.
Severe corrosion occurs when hydrochloric acid, hydrofluoric acid, etc. are mixed in. For this reason, the environment in which it can be used is severely restricted. Ti・or Ti
Does the alloy have sufficient corrosion resistance in various acid solutions including nitric acid, or in acids containing hydrochloric acid, hydrofluoric acid, etc., or reducing acid solutions such as phosphoric acid and sulfuric acid? It has poor corrosion resistance, and as a result, the environment in which it can be used is severely restricted. In areas or environments where metal materials are difficult to adapt to, rubber linings or resin linings are used, which have the disadvantage of being sensitive to high temperature environments and having poor heat transfer. Although Zr, Nb, and Ta have sufficient corrosion resistance in acid solutions with a wide range of compositions, they are very expensive materials, so it is difficult to apply them to a wide range of large-scale equipment.
高Ｃｒ系合金あるいはＮｉ−Ｃｒ系合金は、加工性に乏
しく、撹拌機の羽根のような複雑な形状のを有する構造
物への適応は困難であり、塩酸等の不純物混入に対して
も充分な耐食性を持っておらす、ステンレス鋼と同様に
使用環境にかなりの制限を受ける。本発明の耐酸材料、
即ち、モリブデンを２から３０重量％含有し、かつルテ
ニウム、プラチナ、パラジウムからなる元素のうち少な
くとも１種以上の金属を合計で０．１から１０重二２δ
含有し残部か実質的にクロムからなる耐酸材料は、Ｚ
ｒＳＮｂ、Ｔａに比較すると材料コストもはるかに低く
、高温高濃度の極めて苛酷な環境下においても耐食性か
高く、かつ加工性のよいものである。High Cr alloys or Ni-Cr alloys have poor workability and are difficult to be applied to structures with complex shapes such as stirrer blades, and are also difficult to apply to structures with complex shapes such as stirrer blades. It has excellent corrosion resistance, but like stainless steel, it is subject to considerable limitations in the environment in which it can be used. Acid-resistant material of the present invention,
That is, it contains 2 to 30% by weight of molybdenum and at least one metal selected from the elements consisting of ruthenium, platinum, and palladium in a total of 0.1 to 10 times
The acid-resistant material containing Z
Compared to rSNb and Ta, it has a much lower material cost, has high corrosion resistance even under extremely harsh environments of high temperature and high concentration, and has good workability.
更に、高温、高濃度のギ酸、酢酸等のプラントにおいて
はＴｉあるいは高Ｃｒ系合金等が用いられているが、蒸
留塔のような高温、高濃度の条件では腐食が激しく、こ
のため材料の消耗か大きくプラントの寿命が著しく短い
。しかし、本発明の耐酸材料は、これらの有機酸中にお
いても高耐食性を有しており、多量の塩類の混入した環
境においても高耐食性を維持する。Furthermore, Ti or high Cr alloys are used in plants that produce high-temperature, high-concentration formic acid, acetic acid, etc., but they are subject to severe corrosion under high-temperature, high-concentration conditions such as in distillation columns, resulting in material consumption. The life of the plant is extremely short. However, the acid-resistant material of the present invention has high corrosion resistance even in these organic acids, and maintains high corrosion resistance even in an environment containing a large amount of salts.
更に、従来、塩酸の用いられるプラントにおいてはＴａ
あるいはＮ１合金等が用いられているか、コスト等の問
題があり大型機器への適応に際してはかなり制限がある
ため、高級ステンレス鋼のような材料を使用しなくては
ならない場合も多くある。このような材料では腐食が激
しく、このため材料の消耗か大きくプラントの寿命か著
しく短い。Furthermore, in plants that conventionally use hydrochloric acid, Ta
Alternatively, materials such as N1 alloy are used, or materials such as high-grade stainless steel must be used in many cases, as there are considerable restrictions on application to large equipment due to issues such as cost. Such materials are subject to severe corrosion, resulting in material consumption and a significantly shortened plant life.
しかし、本発明の耐酸材料は塩酸中においても、高級ス
テンレス鋼以上の高耐食性を￥了しているため、プラン
トの長寿命化が図れると同時に大幅なコストダウンも期
待できるものである。However, since the acid-resistant material of the present invention has higher corrosion resistance than high-grade stainless steel even in hydrochloric acid, it can be expected to extend the life of the plant and at the same time significantly reduce costs.
本発明の耐酸材料自体、伝熱もよく、耐食性も著しく高
いため、グラスライニング、テフロンライニングせすし
て、各種耐酸材料として使用可能である。このように本
発明はプラント用材料として非常に優れたものである。The acid-resistant material of the present invention itself has good heat transfer and extremely high corrosion resistance, so it can be used as a variety of acid-resistant materials with glass lining or Teflon lining. As described above, the present invention is extremely excellent as a material for plants.
また、従来の耐酸材料に本発明の耐酸材料をライニング
、溶射等を施し使用することも本発明の一実施態様であ
る。It is also an embodiment of the present invention to use a conventional acid-resistant material by lining, thermal spraying, etc. with the acid-resistant material of the present invention.
［問題を解決するための手段］
本発明の、モリブデンを２から３０重量％含有し、かつ
ルテニウム、プラチナ、パラジウムから少なくとも１種
以上の金属を合計でＯ，］から１１重量％含有し残部か
実質的にクロムからなる耐酸材料は、従来にはない新し
い組成のＣｒ基合金であり、従来公知の金属Ｃｒあるい
はＣｒ基合金と比較して、加工性も良好である。そして
、さらに各種酸中において非常に高い耐食性を有し、塩
酸などのハロゲン化物の混入した無機酸あるいは有機酸
に対しても充分な耐食性を持つものである。[Means for Solving the Problem] The present invention contains 2 to 30% by weight of molybdenum, and a total of 11% by weight of at least one metal from ruthenium, platinum, and palladium, with the balance remaining The acid-resistant material consisting essentially of chromium is a Cr-based alloy with a new composition that has never existed before, and has good workability compared to conventionally known metal Cr or Cr-based alloys. Furthermore, it has extremely high corrosion resistance in various acids, and has sufficient corrosion resistance against inorganic acids or organic acids mixed with halides such as hydrochloric acid.
酸としては硫酸、硝酸、リン酸、塩酸、ギ酸、酢酸ある
いは各種混酸等の酸があり、不純物としてはＮａＣ１、
ＫＣＩ等の無機塩、フッ酸、塩酸等のハロゲン化水素か
ある。Acids include sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid, formic acid, acetic acid, and various mixed acids, and impurities include NaCl,
Examples include inorganic salts such as KCI, and hydrogen halides such as hydrofluoric acid and hydrochloric acid.
以下に、本発明の詳細な説明する。The present invention will be explained in detail below.
［作用コ
本発明の耐酸材料は、耐食性を向上させるため、モリブ
デンを含有し、かつルテニウム、プラチナあるいはパラ
ジウムからなる金属を少なくとも１種以上含有すること
が必要であり、含有量はモリブデンで２重量％以上、ル
テニウム、プラチナ、パラジウムのうちから少なくとも
１種以上の元素の合計で０．１重量％以上か必要であり
さらに好ましくはモリブデンで５重量％以上、ルテニウ
ム、プラチナ、パラジウムのうちから少なくとも１種以
上の元素の合計で０．５重量％以上が必要である。含有
量がモリブデンで２重量％、ルテニウム、プラチナ、パ
ラジウムのうちから少なくとも１種以上の元素の合計で
０．１重量％より低い場合は、十分な耐食性を期待する
ことかできず本発明の目的は達成されない。さらに含有
量かモリブデンで３０重量％以上、ルテニウム、プラチ
ナ、パラジウムで添加される１種以上の元素の合計で１
０重量％以上では添加量に対する性能向上がみられず、
機械加工に悪影響を及ぼし、価格的にも高価なものとな
ってしまう。また、これと同時に、母材となる金属クロ
ムあるいは、モリブデン、ルテニウムパラジウム、プラ
チナの純度は、９９，９重量％以上が好ましく、不純物
が極端に多いものでは、加工性か悪く、溶接による材料
劣化を生じる可能性がある。これらのことから、本発明
では、モリブデンの含有量は２重量％以上３０重量％以
下で、同時にルテニウム、プラチナ、パラジウムの含有
量は添加される少なくとも１種以上の元素の合計で０．
１重量％以上１０重量９・６以下のものが必要であり、
さらに好ましくは母材の金属粉末の純度が９９．９％以
上であることが望ましい。[Function] In order to improve corrosion resistance, the acid-resistant material of the present invention must contain molybdenum and at least one metal consisting of ruthenium, platinum, or palladium, and the content is 2% molybdenum by weight. % or more, at least 0.1% by weight or more of at least one element selected from ruthenium, platinum, and palladium, more preferably 5% or more by weight of molybdenum, and at least one element selected from ruthenium, platinum, and palladium. The total content of more than one species is required to be 0.5% by weight or more. If the content is lower than 2% by weight of molybdenum and 0.1% by weight in total of at least one element selected from ruthenium, platinum, and palladium, sufficient corrosion resistance cannot be expected and the objective of the present invention is is not achieved. In addition, the total content of molybdenum is 30% by weight or more, and one or more elements added such as ruthenium, platinum, and palladium is 1
At 0% by weight or more, no improvement in performance was observed with respect to the amount added.
This adversely affects machining and makes the product expensive. At the same time, the purity of the metal chromium, molybdenum, ruthenium palladium, or platinum used as the base material is preferably 99.9% by weight or more, and if it contains extremely many impurities, the workability will be poor and the material will deteriorate during welding. may occur. For these reasons, in the present invention, the molybdenum content is 2% by weight or more and 30% by weight or less, and at the same time, the content of ruthenium, platinum, and palladium is 0.0% in total of at least one or more added elements.
Must be 1% by weight or more and 10% by weight or less and 9.6% or less,
More preferably, the purity of the metal powder of the base material is 99.9% or more.
本発明の耐酸材料は、タンク、反応器、熱交換器、配管
等の各種酸水溶液を用いるプラントに従来から用いられ
ている材料に代って用いられる。The acid-resistant material of the present invention can be used in place of materials conventionally used in plants that use various acid aqueous solutions, such as tanks, reactors, heat exchangers, and piping.
更に、特徴的なことは、本発明材料はクラッドやライニ
ング材としても使用が可能であることである。さらに本
発明は、これら化学プラント用に限定されるものでなく
、耐酸性の要求される部品あるいは容器等への応用も可
能である。Furthermore, a characteristic feature is that the material of the present invention can also be used as a cladding or lining material. Furthermore, the present invention is not limited to use in these chemical plants, but can also be applied to parts or containers that require acid resistance.
本発明の耐酸材料としての素材の製法は、出発原料とし
ては、クロム、ルテニウム、モリブデン、パラジウム、
プラチナも全て好ましくは純度９９゜９％以上の高純度
金属粉末が必要であり、かかる高純度の金属クロム粉末
は、クロム塩溶液を電解して得た金属クロム、又はクロ
ム塩溶液を溶媒抽出法により精製し、得られたクロム塩
溶液若しくはこの溶液から得たクロム塩を酸化してクロ
ム酸を水素還元法などにより還元して得た金属クロムを
粉砕することにより得られる。このようにして得られた
金属クロム粉末を２から３０重量％のモリブデンと合計
が０．１から１０重量％のルテニウム、パラジウム、プ
ラチナのうち少なくとも１種以上の元素とともに耐真空
性、耐熱性を有した密封容器に封入する。この容器は特
にその材質、形状とも厳密な制限を受けるものではない
が、経済性を考慮するならばステンレス製、又は、銅製
の容器か用いられる。また、この容器の形状は所望の圧
延体の形状により適宜決定される・この方法では金属粉
末を密封容器に封入後ＩＱ−５ｍｍＨｇ以下まで真空排
気を行なう。The method for producing the material as the acid-resistant material of the present invention uses chromium, ruthenium, molybdenum, palladium,
Platinum also requires high-purity metal powder, preferably with a purity of 99.9% or higher, and such high-purity metal chromium powder can be obtained by electrolyzing a chromium salt solution or by solvent extraction of a chromium salt solution. It is obtained by pulverizing metallic chromium obtained by oxidizing the chromium salt solution obtained by purifying the chromium salt solution or by oxidizing the chromium salt obtained from this solution and reducing the chromic acid by a hydrogen reduction method or the like. The metallic chromium powder obtained in this way is combined with 2 to 30% by weight of molybdenum and at least one element among ruthenium, palladium, and platinum in a total of 0.1 to 10% by weight to improve vacuum resistance and heat resistance. Place it in a sealed container. The material and shape of this container are not strictly limited, but if economical considerations are taken into consideration, stainless steel or copper containers may be used. In addition, the shape of this container is appropriately determined depending on the desired shape of the rolled product. In this method, metal powder is sealed in a sealed container and then evacuated to below IQ-5 mmHg.
次に上記真空処理を行なった後６００〜１０００℃で熱
間みぞロール圧延を行なう。みぞ型ロールとしては汎用
のもので良いが通常は二段圧延機が用いられる。この温
度範囲では金属クロム中への窒素の固溶度が３〜１７ｐ
ｐｍと低く再結晶を抑制することができる。また、圧延
率を５０〜８０％とすることによりち密な組織を有する
成型体が得られる。Next, after performing the above vacuum treatment, hot groove roll rolling is performed at 600 to 1000°C. Although a general-purpose groove roll may be used, a two-high rolling mill is usually used. In this temperature range, the solid solubility of nitrogen in metallic chromium is 3 to 17 p.
Recrystallization can be suppressed at a low pm. Further, by setting the rolling rate to 50 to 80%, a molded product having a dense structure can be obtained.
加熱圧延後の冷却は徐冷が好ましい。急冷すると内部の
クロム合金組織に不均一な熱応力が加わり、クラックが
発生する恐れがあるからである。次に得られた圧延体を
８００〜１０００℃で焼鈍することにより組織の均一化
および軟化を行なう。この焼鈍時間は特に限定されない
か、通常は１時間以上行なわれる。本発明の耐酸材料は
このような方法で得られるか、製法としてはこの方法に
限定されるものではなく、高周波雰囲気炉あるいは高周
波アーク炉等の種々の溶解法を用いインゴットを作製し
熱間圧延等の塑性加工を用い得ることも可能である。The cooling after hot rolling is preferably slow cooling. This is because rapid cooling applies uneven thermal stress to the internal chromium alloy structure, which may cause cracks to occur. Next, the obtained rolled body is annealed at 800 to 1000°C to homogenize and soften the structure. This annealing time is not particularly limited, and is usually performed for one hour or more. The acid-resistant material of the present invention can be obtained by such a method, but the manufacturing method is not limited to this method, and ingots are produced using various melting methods such as a high-frequency atmosphere furnace or a high-frequency arc furnace, and hot-rolled. It is also possible to use plastic working such as.
［実施例］
以下、実施例に基き説明するが、これらの実施例は本発
明を同等限定するものではない。[Examples] The present invention will be described below based on Examples, but these Examples do not limit the present invention in the same way.
実施例１〜５および比較例１〜３ 第１表に示す組成を有する本発明のＣｒ−Ｍ。Examples 1-5 and Comparative Examples 1-3 Cr-M of the present invention having the composition shown in Table 1.
−Ｐｄ、Ｃｒ−Ｍｏ−ＲｕＳＣｒ−ＭＯ−Ｐ ｔ。-Pd, Cr-Mo-RuSCr-MO-Pt.
Ｃｒ−Ｍｏ−Ｒｕ−Ｐｄ合金および、比較材を以下のよ
うな製法により作製した。A Cr-Mo-Ru-Pd alloy and a comparative material were produced by the following manufacturing method.
純度９９．９％以上のクロム、ルテニウム、パラジウム
、プラチナ、モリブデン金属粉末を用い第１表に示す組
成に混合し、ステンレス製の密封容器に封入し、１０−
”ｍｍＨｇになるまで真空排気を行なった。Using chromium, ruthenium, palladium, platinum, and molybdenum metal powders with a purity of 99.9% or more, they were mixed to the composition shown in Table 1, sealed in a stainless steel container, and mixed with 10-
Vacuum evacuation was performed until the temperature reached ``mmHg.''
次に８００℃、圧延率７００ｏて熱間みそロール圧延を
行い得られた圧延体を１０００℃、１時間で焼鈍した。Next, hot miso roll rolling was performed at 800° C. and a rolling rate of 700°, and the resulting rolled body was annealed at 1000° C. for 1 hour.
この後２ｃｍＸ３ｃｍの大きさのテストピースに加工し
た。Thereafter, it was processed into a test piece with a size of 2 cm x 3 cm.
加工した各テストピースを表に示す濃度の塩酸、ギ酸、
リン酸、及び硫酸の水溶液に浸漬し、各々の平均腐食速
度を求めた。その結果を第２表に示す。Each processed test piece was exposed to hydrochloric acid, formic acid,
It was immersed in aqueous solutions of phosphoric acid and sulfuric acid, and the average corrosion rate of each was determined. The results are shown in Table 2.
［発明の効果］
本発明の耐酸材料は、従来までの材料、特に焼結クロム
、Ｔｉあるいは高クロム合金に比べて極めて耐食性に優
れ、新規の装置設計が可能となると同時に装置の長寿命
化が計れる。また、耐食性の向上にともなう装置の信頼
性の向上から、反応の際の高温、高濃度化に伴う運転条
件の変更に充分対応が可能となるとともにこれによる反
応効率の向上、製品のコストダウンか可能となる。さら
に、本発明の耐酸材料は、Ｔａ、Ｎｂ、Ｚ ｒ等の高級
金属材料と比べるとはるかに低コストであり、また、従
来品では不可能であった薄板への加工か可能であるため
、圧接材、クラッド祠、ライニシグ材として用いること
による、材料としての価格の大幅な低減あるいは、さら
に高い加工性を有した材料との組合わせによる加工性と
耐食性の双方の飛躍的向上をはかることか可能となる。[Effects of the Invention] The acid-resistant material of the present invention has extremely superior corrosion resistance compared to conventional materials, especially sintered chromium, Ti, or high chromium alloys, making it possible to design new equipment and at the same time extending the life of the equipment. It can be measured. In addition, the improved reliability of the equipment due to improved corrosion resistance makes it possible to fully respond to changes in operating conditions associated with high temperatures and high concentrations during reactions, and this improves reaction efficiency and reduces product costs. It becomes possible. Furthermore, the acid-resistant material of the present invention is much lower in cost than high-grade metal materials such as Ta, Nb, and Zr, and can be processed into thin plates, which was not possible with conventional products. By using it as a pressure welding material, cladding material, and reinishing material, we can significantly reduce the price of the material, or by combining it with materials with even higher workability, we can dramatically improve both workability and corrosion resistance. It becomes possible.
第１表 第２表Table 1 Table 2
Claims (1)
ニウム、プラチナ、パラジウムからなる元素のうち少な
くとも１種以上の金属を合計で０．１から１０重量％含
有し残部が実質的にクロムからなる耐酸材料(1) Contains 2 to 30% by weight of molybdenum, and a total of 0.1 to 10% by weight of at least one metal among the elements consisting of ruthenium, platinum, and palladium, with the remainder substantially consisting of chromium. acid resistant material
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32075190A JPH04191345A (en) | 1990-11-27 | 1990-11-27 | Acid resistant material |
| EP19910301795 EP0446009A1 (en) | 1990-03-06 | 1991-03-05 | Acidproof materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32075190A JPH04191345A (en) | 1990-11-27 | 1990-11-27 | Acid resistant material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04191345A true JPH04191345A (en) | 1992-07-09 |
Family
ID=18124875
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32075190A Pending JPH04191345A (en) | 1990-03-06 | 1990-11-27 | Acid resistant material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04191345A (en) |
-
1990
- 1990-11-27 JP JP32075190A patent/JPH04191345A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1337850C (en) | Corrosion resistant high strength nickel-base alloy | |
| JP3355510B2 (en) | Austenitic alloys and their use | |
| JPS6134498B2 (en) | ||
| US11629393B2 (en) | Niobium-based alloy that is resistant to aqueous corrosion | |
| Rebak et al. | Influence of the environment on the general corrosion rate of alloy 22 (N06022) | |
| US5296054A (en) | Austenitic steel | |
| JPH04191345A (en) | Acid resistant material | |
| CN1315585A (en) | Cheap Ni alloy resisting strong corrosion | |
| JPH03257136A (en) | Acid-proof material | |
| US4050928A (en) | Corrosion-resistant matrix-strengthened alloy | |
| JPS62199744A (en) | Titanium alloy having superior crevice corrosion resistance | |
| JPH02166254A (en) | Acid-resisting material | |
| CA1307138C (en) | Use of a chromium-containing alloy | |
| EP0446009A1 (en) | Acidproof materials | |
| JP7492259B2 (en) | Steel | |
| JPH04224665A (en) | Production of titanium alloy excellent in corrosion resistance | |
| JP4953371B2 (en) | Ni-based alloy excellent in nitric acid corrosion resistance and method for producing the same | |
| JP2002194466A (en) | Nickel based alloy clad steel and its production method | |
| CN117778852A (en) | High-temperature-resistant corrosion-resistant nickel-based alloy hot rolled steel plate and preparation method thereof | |
| CN105821277A (en) | Corrosion-resistant alloy and preparation method thereof | |
| JPS63241134A (en) | Organic acid resistant material | |
| JPS61174346A (en) | Corrosion resisting titanium alloy having superior bendability | |
| TW202206616A (en) | Acid corrosion resistant alloy and method of producing the same | |
| JPS5841345B2 (en) | amorphous amorphous | |
| CN115781102A (en) | Nickel-chromium alloy welding wire and preparation process thereof |