JPH03157358A - Production of o-methylisourea salt - Google Patents
Production of o-methylisourea saltInfo
- Publication number
- JPH03157358A JPH03157358A JP29628689A JP29628689A JPH03157358A JP H03157358 A JPH03157358 A JP H03157358A JP 29628689 A JP29628689 A JP 29628689A JP 29628689 A JP29628689 A JP 29628689A JP H03157358 A JPH03157358 A JP H03157358A
- Authority
- JP
- Japan
- Prior art keywords
- cyanamide
- solution
- weight
- organic liquid
- acid
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- RMAHPRNLQIRHIJ-UHFFFAOYSA-N methyl carbamimidate Chemical class COC(N)=N RMAHPRNLQIRHIJ-UHFFFAOYSA-N 0.000 title claims abstract description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 93
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims abstract description 72
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000007788 liquid Substances 0.000 claims abstract description 29
- MYFXBBAEXORJNB-UHFFFAOYSA-N calcium cyanamide Chemical compound [Ca+2].[N-]=C=[N-] MYFXBBAEXORJNB-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 27
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 27
- 239000007789 gas Substances 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 20
- 239000006185 dispersion Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 27
- 238000000034 method Methods 0.000 abstract description 25
- 239000013078 crystal Substances 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 39
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 17
- 239000011575 calcium Substances 0.000 description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- SADHVOSOZBAAGL-UHFFFAOYSA-N 3-(trifluoromethoxy)aniline Chemical compound NC1=CC=CC(OC(F)(F)F)=C1 SADHVOSOZBAAGL-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 4
- 235000011116 calcium hydroxide Nutrition 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- MVXMNHYVCLMLDD-UHFFFAOYSA-N 4-methoxynaphthalene-1-carbaldehyde Chemical compound C1=CC=C2C(OC)=CC=C(C=O)C2=C1 MVXMNHYVCLMLDD-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- 235000012255 calcium oxide Nutrition 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 238000006358 imidation reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000005121 nitriding Methods 0.000 description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methyl urea Chemical compound CNC(N)=O XGEGHDBEHXKFPX-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- LHHACTKLABTCQF-UHFFFAOYSA-N [amino(hydroxy)methylidene]-methylazanium;chloride Chemical compound Cl.CNC(O)=N LHHACTKLABTCQF-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 229940023913 cation exchange resins Drugs 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- CEIPQQODRKXDSB-UHFFFAOYSA-N ethyl 3-(6-hydroxynaphthalen-2-yl)-1H-indazole-5-carboximidate dihydrochloride Chemical compound Cl.Cl.C1=C(O)C=CC2=CC(C3=NNC4=CC=C(C=C43)C(=N)OCC)=CC=C21 CEIPQQODRKXDSB-UHFFFAOYSA-N 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- MUDVUWOLBJRUGF-UHFFFAOYSA-N (c-methoxycarbonimidoyl)azanium;chloride Chemical compound Cl.COC(N)=N MUDVUWOLBJRUGF-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000005997 Calcium carbide Substances 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UFONUKZQWFSQLP-UHFFFAOYSA-N [N].NC#N Chemical compound [N].NC#N UFONUKZQWFSQLP-UHFFFAOYSA-N 0.000 description 1
- VYWQTJWGWLKBQA-UHFFFAOYSA-N [amino(hydroxy)methylidene]azanium;chloride Chemical compound Cl.NC(N)=O VYWQTJWGWLKBQA-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- MDFRYRPNRLLJHT-UHFFFAOYSA-N methyl carbamimidate;sulfuric acid Chemical compound COC(N)=N.OS(O)(=O)=O MDFRYRPNRLLJHT-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/70—Compounds containing any of the groups, e.g. isoureas
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、医薬、農薬及び工業用薬品の中間体として、
有用な０−メチルイソ尿素塩の新規な製造法に関し、詳
しくは、メタノールを含有する有機液体中で石灰窒素か
らシアナミドを遊離させ、得られたシアナミド溶液から
シアナミドを単離することなしに、該シアナミド溶液に
酸を反応させて直ちに０−メチルイソ尿素塩を生成させ
る方法に関し、更に詳しくは、石灰窒素を、メタノール
を含有してなる有機液体中に分散させ、得られた分散液
の中に炭酸ガスを導入することにより該有機液体中のシ
アナミド溶液を生成させ、次いで該シアナミド溶液に酸
を添加することを特徴とするＯ−メチルイソ尿素塩の製
法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention is directed to the use of intermediates for pharmaceuticals, agricultural chemicals, and industrial chemicals.
A novel method for producing useful 0-methylisourea salts is described in detail, in which cyanamide is liberated from lime nitrogen in an organic liquid containing methanol, and cyanamide is prepared without isolating the cyanamide from the resulting cyanamide solution. Regarding the method of immediately producing 0-methylisourea salt by reacting a solution with an acid, more specifically, lime nitrogen is dispersed in an organic liquid containing methanol, and carbon dioxide gas is added to the resulting dispersion. The present invention relates to a method for producing an O-methylisourea salt, characterized in that a cyanamide solution is produced in the organic liquid by introducing the organic liquid, and then an acid is added to the cyanamide solution.
従来、０−メチルイソ尿素塩の製法としては、シアナミ
ドの結晶など、シアナミド単離体をメタノール中に溶解
させて、得られたシアナミドのメタノール溶液に塩化水
素や硫酸などの酸を反応させる方法が知られている。Conventionally, a known method for producing 0-methylisourea salt is to dissolve cyanamide isolates such as cyanamide crystals in methanol and react the resulting methanol solution of cyanamide with an acid such as hydrogen chloride or sulfuric acid. It is being
上記の方法において使用するシアナミドの結晶等シアナ
ミドの単離体を製造する方法としては、従来より工業的
には、水中にスラリー状に分散した石灰窒素に炭酸ガス
を反応させ、得られたシアナミド水溶液を濃縮乾固する
方法が採用されている。Conventionally, as a method for producing cyanamide isolates such as cyanamide crystals used in the above method, an aqueous cyanamide solution is produced by reacting carbon dioxide gas with lime nitrogen dispersed in a slurry form in water. A method of concentrating and drying is used.
この方法では、石灰窒素は、次式（１）のように水と反
応し、
２ＣａＣＮ、＋２Ｈ，Ｏ−＝ Ｃａ（ＨＮＣＮ）、＋Ｃ
ａ（ＯＨ）、−−（１）次いで、生成したＣａ（ＨＮＣ
Ｎ）ｌＩ又はＣａ （０）！Ｌと炭酸ガスとが、夫々、
次式（２）及び（３）のように反応すると考えられてい
る。In this method, lime nitrogen reacts with water as shown in the following equation (1), 2CaCN, +2H,O-=Ca(HNCN), +C
a(OH), --(1) Then, the generated Ca(HNC
N) lI or Ca (0)! L and carbon dioxide are each
It is thought that the reaction occurs as shown in the following formulas (2) and (3).
Ｃａ（ＯＨ）２ ＋ＣＯ，→ Ｈ，０＋ＣａＣ０，−−
＝−−−−−＜２）Ｃａ（ＨＮＣＮ）、＋ＣＯ，＋Ｈ，
０→２Ｈ１ｌＮＣＮ＋ＣａＣ０，＝４３）これら反応式
（１）〜（３）を総合すると、上記の製法は結局次式（
４）、
ＣａＣＮ、＋ＧＯ，−ｔ４１，０ →Ｈ，ＮＣＮ＋Ｃａ
Ｃ０３−−−−−−ぺ４）に従っているものと考えるこ
とができる。Ca(OH)2 +CO, → H,0+CaC0,--
=−−−−−<2) Ca(HNCN), +CO, +H,
0→2H11NCN+CaC0,=43) When these reaction formulas (1) to (3) are combined, the above production method ends up being the following formula (
4), CaCN, +GO, -t41,0 →H, NCN+Ca
It can be considered that this is in accordance with C03--P4).
上記反応式によっても明らかなように、水中に石灰窒素
を分散させてシアナミドを製造する方法では、先ず式（
１）のように水酸化カルシウムが生成するため、シアナ
ミドの遊離化反応は通常アルカリ性の水性媒体中で進行
することになるので、シアナミドの１部が三量化してジ
シアンジアミドを副成し易い。また、生成したシアナミ
ド水溶液より濃縮乾固によりシアナミドを単離する過程
で、少量の溶存カルシウムも濃縮されて水溶液が次第に
アルカリ性を増し、シアナミドの１部がさらに三量化し
てジシアンジアミドとなり易い。この反応は、時には爆
発的に起こることがあって極めて危険なため、水溶液中
の溶存カルシウム量はできるだけ減少させておく必要が
あり、そのために煩雑な操作が要求される。さらに、こ
のような副生ジシアンジアミドをシアナミドから分離す
ることは一般に容易ではないので、上記の製法で得られ
るシアナミドには、ジシアンジアミドの夾雑が避けられ
ず、純度９２重量％を越える高純度のシアナミドを工業
的に製造することは極めて困難である。As is clear from the above reaction formula, in the method of producing cyanamide by dispersing lime nitrogen in water, first the formula (
Since calcium hydroxide is produced as in 1), the cyanamide liberation reaction usually proceeds in an alkaline aqueous medium, so that a portion of cyanamide tends to trimerize and form dicyandiamide as a by-product. In addition, in the process of isolating cyanamide from the produced aqueous cyanamide solution by concentration to dryness, a small amount of dissolved calcium is also concentrated, the aqueous solution gradually becomes more alkaline, and a portion of the cyanamide is likely to further trimerize to form dicyandiamide. Since this reaction sometimes occurs explosively and is extremely dangerous, it is necessary to reduce the amount of dissolved calcium in the aqueous solution as much as possible, which requires complicated operations. Furthermore, since it is generally not easy to separate such by-product dicyandiamide from cyanamide, the cyanamide obtained by the above production method is inevitably contaminated with dicyandiamide, and high-purity cyanamide with a purity exceeding 92% by weight cannot be avoided. It is extremely difficult to manufacture industrially.
更にまた、単離したシアナミド粉末はその貯蔵時の安定
性も必ずしも十分とはいい難く、経時的に三量化してジ
シアンジアミドの含有量が増加したり、場合によっては
この二量化反応が爆発的に起こる危険性もあり、冷蔵庫
などによる低温保存が不可欠である。このように、シア
ナミドの単離方法及びその貯蔵には多くのデリケートで
煩雑な開運があり、従って、シアナミド単離体を用いて
〇−メチルイソ尿素を製造する方法は、コスト高となら
ざるを得なかった。Furthermore, the stability of isolated cyanamide powder during storage is not necessarily sufficient, and the content of dicyandiamide may increase over time due to trimerization, and in some cases, this dimerization reaction may be explosive. There is a risk that this may occur, so it is essential to store it at a low temperature, such as in a refrigerator. As described above, the method of isolating cyanamide and its storage involves many delicate and complicated steps, and therefore, the method of producing 0-methylisourea using isolated cyanamide is inevitably expensive. There wasn't.
本発明者等は、上記のごとく製造上及び貯蔵上に多く問
題を有するシアナミド単離体を使用せずに０−メチルイ
ソ尿素を製造する方法について鋭意研究を行った結果、
従来はとんど検討されたことがない方法、すなわち、メ
タノール中に分散させた石灰窒素に炭酸ガスを反応させ
ることにより、ジシアンジアミド等の不純物の含有が極
めて少ないシアナミドのメタノール溶液を得、次いでシ
アナミドを単離せずにこの溶液をそのまま用い、これに
硫酸などの酸を添加反応させることによって、高収率で
高純度の０−メチルイソ尿素塩を安全且つ容易に製造し
得ることを見出だし、更に研究を進めた結果、本発明を
完成するに至った。The present inventors have conducted intensive research on a method for producing 0-methylisourea without using cyanamide isolate, which has many problems in production and storage as described above.
A methanol solution of cyanamide with extremely low content of impurities such as dicyandiamide is obtained by reacting carbon dioxide gas with lime nitrogen dispersed in methanol, which has never been considered in the past. They have discovered that by using this solution as it is without isolating it and reacting it with an acid such as sulfuric acid, it is possible to safely and easily produce a high-yield, high-purity 0-methylisourea salt, and further As a result of research, we have completed the present invention.
本発明は、石灰窒素を、メタノールを含有してなる有機
液体中に分散させ、得られた分散液の中に炭酸ガスを導
入することにより該有機液体中のシアナミド溶液を生成
させ、次いで該シアナミド溶液に酸を添加することを特
徴とする０−メチルイソ尿素塩の製法を提供するもので
ある。The present invention involves dispersing lime nitrogen in an organic liquid containing methanol, introducing carbon dioxide gas into the resulting dispersion to generate a cyanamide solution in the organic liquid, and then dispersing the cyanamide in the organic liquid. The present invention provides a method for producing an 0-methylisourea salt, which is characterized by adding an acid to a solution.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
シアナミド′ 工
本発明方法は先ず、石灰窒素を、メタノールを含有して
なる有機液体中に分散させ、得られた分散液中に炭酸ガ
スを導入することにより、有機液体中のシアナミド溶液
を生成させるシアナミド遊離化工程を有する。Cyanamide Process The method of the present invention involves first dispersing lime nitrogen in an organic liquid containing methanol, and introducing carbon dioxide gas into the resulting dispersion to produce a cyanamide solution in the organic liquid. It has a liberating process.
上記の原料石灰窒素は、カルシウムカーバイドを窒化炉
で窒化することによって工業的に生産されている。石灰
窒素は、カルシウムシアナミドの外に窒化時副生するグ
ラファイト状炭素及び生石灰等の不純物を含んでいる。The above raw material lime nitrogen is industrially produced by nitriding calcium carbide in a nitriding furnace. In addition to calcium cyanamide, lime nitrogen contains impurities such as graphitic carbon and quicklime that are produced as by-products during nitriding.
一般に市販の石灰窒素は窒素含有率が２０〜２７重量％
であり、シアナミド憇窒素含有率が１９〜２６重量％で
ある。本発明の製法においては、石灰窒素を必要に応じ
て粉砕し、タイラー標準篩の２００メツシュ通過粒分が
５０重量％以上になるようにして用いられる。Generally, commercially available lime nitrogen has a nitrogen content of 20 to 27% by weight.
and the cyanamide nitrogen content is 19 to 26% by weight. In the production method of the present invention, lime nitrogen is pulverized if necessary so that the amount of particles passing through a 200-mesh Tyler standard sieve is 50% by weight or more.
本発明の製造法に用いる分散媒である有機液体は、メタ
ノールを含有してなる。該有機液体は、メタノールから
実質的になっていてもよいが、得られるシアナミド溶液
の純度及び収率、並びに、引き続いて行なわれる０−メ
チルイソ尿素化（イミデート化）反応を阻害しない程度
に、必要に応じ更なる有機溶媒を含んでいてもよい。The organic liquid that is the dispersion medium used in the production method of the present invention contains methanol. The organic liquid may consist essentially of methanol, but as long as it does not interfere with the purity and yield of the resulting cyanamide solution and the subsequent 0-methylisoureaation (imidation) reaction. It may contain an additional organic solvent depending on the situation.
上記の更なる有機溶媒としてはアセトニトリル、ジメチ
ルホルムアミド、酢酸エチル、アセトン、テトラヒドロ
フラン等を例示することができる。Examples of the above-mentioned further organic solvents include acetonitrile, dimethylformamide, ethyl acetate, acetone, and tetrahydrofuran.
本発明においては、分散媒である有機液体中における石
灰窒素分散液の石灰窒素の濃度は、仕込時で、好ましく
は５〜２５重量％、より好ましくは１５〜２０重量％で
ある。In the present invention, the concentration of lime nitrogen in the lime nitrogen dispersion in the organic liquid that is the dispersion medium at the time of charging is preferably 5 to 25% by weight, more preferably 15 to 20% by weight.
本発明方法のシアナミド遊離化工程においては、上記の
石灰窒素の分散液中に炭酸ガスを導入することにより、
有機液体中のシアナミド溶液としてシアナミドが生成す
る。その反応機構は必ずしも詳らかではないが、本発明
者等は次の反応式に従って反応するものと推定している
。In the cyanamide liberating step of the method of the present invention, by introducing carbon dioxide gas into the above lime nitrogen dispersion,
Cyanamide is produced as a solution of cyanamide in an organic liquid. Although the reaction mechanism is not necessarily clear, the present inventors estimate that the reaction occurs according to the following reaction formula.
ＣａＣＮ、 ＋２ＣＨ，ＯＨ＋ ２ＧＯ。CaCN, +2CH, OH+2GO.
従って、炭酸ガスの使用量は、石灰窒素中のカルシウム
分に対して２当量以上であるのが好ましい。Therefore, the amount of carbon dioxide used is preferably 2 equivalents or more relative to the calcium content in lime nitrogen.
本発明で用いる炭酸ガスは必ずしも高純度である必要は
なく、窒素、酸素、空気等この反応系に対する不活性気
体で適宜希釈されていてもよい。The carbon dioxide gas used in the present invention does not necessarily have to be of high purity, and may be diluted with an inert gas for this reaction system, such as nitrogen, oxygen, or air.
しかし、炭酸ガスのガス中の濃度が余り低過ぎては、メ
タノールがガスに同伴して損失する等の問題が生じるの
で、一般にガス中の炭酸ガス濃度は２０重量％以上、殊
に４０重量％以上が好ましく、またガス中の水分量も２
０重量％以下、好ましくは２重量％以下、殊に０．２重
量％以下である。However, if the concentration of carbon dioxide in the gas is too low, problems such as methanol being lost along with the gas will occur, so the concentration of carbon dioxide in the gas is generally 20% by weight or more, especially 40% by weight. or more is preferable, and the amount of water in the gas is also 2
It is not more than 0% by weight, preferably not more than 2% by weight, especially not more than 0.2% by weight.
炭酸ガスの導入方法としては、特に限定されるものでは
なく、有機液体中に直接吹き込む方法、予めメタノール
や前記更なる有機溶媒中に炭酸ガスを溶解させて溶液と
して添加する方法などを採用することができるが、操作
の容易性等の理由から直接炭酸ガスを吹き込むのが好ま
しい。このような、炭酸ガス吹込みによる反応は、０．
１〜１０ｋｇ／ａｍ’の圧力下、好ましくは大気圧下で
、−１０〜３０℃、好ましくは０〜２０℃の温度で行わ
れる。反応温度が該上限値以下であれば、得られるシア
ナミド溶液中の不純物濃度を低く抑えることができるの
で好ましく、一方該下限値以上であれば反応操作も容易
であり、適度な反応速度で反応が進行するので好ましい
。The method of introducing carbon dioxide gas is not particularly limited, and methods such as directly blowing it into the organic liquid, dissolving carbon dioxide gas in methanol or the above-mentioned further organic solvent in advance, and adding it as a solution may be adopted. However, it is preferable to directly blow carbon dioxide gas for reasons such as ease of operation. Such a reaction by blowing carbon dioxide gas is 0.
It is carried out under a pressure of 1 to 10 kg/am', preferably atmospheric pressure, and at a temperature of -10 to 30°C, preferably 0 to 20°C. If the reaction temperature is below the upper limit, it is preferable because the concentration of impurities in the obtained cyanamide solution can be kept low, while if it is above the lower limit, the reaction operation is easy and the reaction can be carried out at an appropriate reaction rate. This is preferable because it progresses.
炭酸ガス導入による反応の終了後、泥状の反応分散液を
常法により濾過して、有機液体中のシアナミド溶液を容
易に取得することができる。After the reaction is completed by introducing carbon dioxide gas, the muddy reaction dispersion liquid is filtered by a conventional method to easily obtain a cyanamide solution in an organic liquid.
本発明方法のシアナミド遊離化工程における反応系の水
含有量（分散媒である有機液体中の水の含有量）は、一
般に２０重量％以下、好ましくは５重量％以下、より好
ましくは３．５重量％以下、さらに好ましくは２゜５重
量％以下、最も好ましく１重量％以下である。反応系の
水の含有量が２０重量％以下と少なくなるに従い、シア
ナミドの二量化によるジシアンジアミドの副生が抑制さ
れるとともに、反応系がゲル化することもないので、該
水の含有量は上記上限値以下であるのが好ましい。The water content of the reaction system in the cyanamide liberating step of the method of the present invention (the content of water in the organic liquid as a dispersion medium) is generally 20% by weight or less, preferably 5% by weight or less, more preferably 3.5% by weight or less. It is less than 2% by weight, more preferably less than 2.5% by weight, and most preferably less than 1% by weight. As the water content of the reaction system decreases to 20% by weight or less, the by-product of dicyandiamide due to dimerization of cyanamide is suppressed, and the reaction system does not gel. It is preferable that it is below the upper limit.
なお反応系中に存在する水は、用いられる有機液体中に
初めから含まれている水や、出発原料の石灰窒素中に含
まれる水及び導入される炭酸ガス中の水分などのほかに
、該石灰窒素中に不純物として含有される生石灰（Ｃａ
ｂ）や水酸化カルシウム［Ｃａ （ＯＨ） 、］などが
次のように有機液体中で炭酸ガスと反応することによっ
て生成する水などが想定されるため、一般に反応系中の
水含有量は経時的に増加する。The water present in the reaction system includes water originally contained in the organic liquid used, water contained in lime nitrogen as a starting material, water in carbon dioxide gas introduced, etc. Quicklime (Ca) contained as an impurity in lime nitrogen
b), calcium hydroxide [Ca (OH) , ], etc. are assumed to be generated by reacting with carbon dioxide gas in an organic liquid as shown below, so the water content in the reaction system generally changes over time. increase.
ＣａＯ＋ ２ＣＨ，ＯＨ＋ ２ＧＯ。CaO+ 2CH, OH+ 2GO.
Ｃａ （ＯＨ）、 ＋ ＣＨ，ＯＨ＋ Ｇｏ。Ca (OH), + CH, OH + Go.
従って、本明細書における反応系の水含有量は、炭酸ガ
ス導入反応の終了時点における反応系の水含有量をいう
。Therefore, the water content of the reaction system in this specification refers to the water content of the reaction system at the end of the carbon dioxide introduction reaction.
反応系の水含有量は以下の方法により測定した。The water content of the reaction system was measured by the following method.
先ず反応系から採取した反応分散液を遠心分離濾遇して
、有機液体不溶分を除去し、得られた濾液（有機液体溶
液）をガスクロマトグラフィー分析［以下、ＧＣ分析と
略称することがある］（Ｔ０ｎ法）することにより該濾
液中の水含有量を測定し、反応系の水含有量とした。First, the reaction dispersion liquid collected from the reaction system is centrifuged and filtered to remove organic liquid insoluble components, and the obtained filtrate (organic liquid solution) is subjected to gas chromatography analysis [hereinafter sometimes abbreviated as GC analysis]. ] (T0n method), the water content in the filtrate was measured and taken as the water content of the reaction system.
得られたシアナミド溶液は、わずかに溶存するカルシウ
ムイオン等の作用によって保存中にゲル化を起こす場合
もあるので、必要に応じ、該溶液に酸を少量添加して溶
液を安定化することができる。このような酸としては、
リン酸、硫酸、硝酸、塩酸などの無機酸；酢酸、蓚酸な
どの有機酸；スルホン酸型陽イオン交換樹脂などの陽イ
オン交換樹脂：等を例示することができ、中でもリン酸
が好適に用いられる。これらの酸の添加量は、該シアナ
ミド溶液中の溶存カルシウムに対して約１当量であるの
が好ましい。The obtained cyanamide solution may undergo gelation during storage due to the action of slightly dissolved calcium ions, so if necessary, a small amount of acid can be added to the solution to stabilize the solution. . Such acids include
Examples include inorganic acids such as phosphoric acid, sulfuric acid, nitric acid, and hydrochloric acid; organic acids such as acetic acid and oxalic acid; and cation exchange resins such as sulfonic acid type cation exchange resins; among them, phosphoric acid is preferably used. It will be done. The amount of these acids added is preferably about 1 equivalent to the dissolved calcium in the cyanamide solution.
かくして得られたシアナミド溶液は、必要に応じて濃縮
し又はメタノールや前記の更なる有機溶媒で希釈して所
望のシアナミド濃度の溶液とし、次のイミデート化反応
工程に使用される。The cyanamide solution thus obtained is concentrated or diluted with methanol or the above-mentioned further organic solvent as necessary to obtain a solution with a desired cyanamide concentration, and used in the next imidation reaction step.
なお、シアナミド溶液を濾別した後の黒色の残渣は水の
添加によって炭酸ガスを発生し、メタノールを分離生成
するので、これらメタノール及び炭酸ガスを常法により
回収して再使用することが可能である。In addition, the black residue after filtering the cyanamide solution generates carbon dioxide gas by adding water, and methanol is separated and produced, so it is possible to recover and reuse these methanol and carbon dioxide gas by conventional methods. be.
イミデート 応工
本発明方法は、前記シアナミド遊離化工程で得られたメ
タノールを含有してなる有機液体中のシアナミド溶液に
酸を添加反応させて０−メチルイソ尿素塩を生成させる
イミデート化工程を有する。Imidate Process The method of the present invention includes an imidate process in which an acid is added to react the cyanamide solution in the methanol-containing organic liquid obtained in the cyanamide liberating process to produce an 0-methylisourea salt.
上記シアナミド溶液中のシアナミド濃度としては、一般
に４０重量％以下、好ましくは３０重量％以下、より好
ましくは２０〜３０重量％であるのがよく、２０〜３０
重量％のシアナミドのメタノール溶液であるのが特に好
ましい。該シアナミド濃度が該上限値以下であれば、得
られるＯ−メチルイソ尿素塩のスラリー粘度が高くなり
過ぎることがないので攪拌に支障を来たすことがなく、
また、２０重量％以上であれば、該０−メチルイソ尿素
の生成収率を高水準に保つことができるので好ましい。The cyanamide concentration in the cyanamide solution is generally 40% by weight or less, preferably 30% by weight or less, more preferably 20 to 30% by weight, and 20 to 30% by weight.
Particularly preferred is a methanol solution of cyanamide in weight percent. If the cyanamide concentration is below the upper limit, the viscosity of the resulting O-methylisourea salt slurry will not become too high, and stirring will not be hindered.
Further, if it is 20% by weight or more, it is preferable because the production yield of the 0-methylisourea can be maintained at a high level.
この工程に用いることのできる酸としては、例えば、塩
化水素などのハロゲン化水素酸、濃硫酸、濃硝酸、濃リ
ン酸（８５重量％以上、好ましくは実質的に１００重量
％のもの）等の無機酸；例えば、メタンスルホン酸、パ
ラトルエンスルホン酸等の有機酸；を挙げることができ
る。これらの酸の水の含有量は極力少ないのがよい。水
の含有量が少なければ、尿素などの副生が抑えられてＯ
−メチルイソ尿素の収率が高くなるので好ましい。Examples of acids that can be used in this step include hydrohalic acids such as hydrogen chloride, concentrated sulfuric acid, concentrated nitric acid, and concentrated phosphoric acid (85% by weight or more, preferably substantially 100% by weight). Inorganic acids; for example, organic acids such as methanesulfonic acid and para-toluenesulfonic acid; The water content of these acids is preferably as low as possible. If the water content is low, by-products such as urea are suppressed and O
- It is preferable because the yield of methyl isourea is high.
このイミデート化反応工程の反応機構は、通常、次のよ
うに進行するものと想定される。The reaction mechanism of this imidation reaction step is generally assumed to proceed as follows.
（但し、ＨＡは酸を表す）
このように、この反応工程において使用される酸の量は
、シアナミド１モルに対して一般に１当量以上であり、
１〜３当量であるのが好ましい。(However, HA represents an acid.) Thus, the amount of acid used in this reaction step is generally 1 equivalent or more per mol of cyanamide,
Preferably it is 1 to 3 equivalents.
但し、酸として濃硫酸を用いる場合には次のような２段
反応になると考えられる。However, when concentrated sulfuric acid is used as the acid, it is thought that the following two-stage reaction will occur.
Ｈ２ＮＣＮ＋ＣＨ，ＯＨ＋）Ｉ、Ｓｏ。H2NCN+CH,OH+)I, So.
一般に、上記（９）の反応は極めて速く、上記（１０）
の反応は緩慢である。このためＯ−メチルイソ尿素の硫
酸塩を得ようとするときには、先ず、シアナミドに対し
て等モルの硫酸を用いて全てのシアナミドをＯ−メチル
イソ尿素の硫酸水素塩とし、次いで次式のように、この
反応系においてアルカリとして作用する化合物（以下、
単にアルカリ性化合物と略称することがある）を添加反
応させることにより目的のＯ−メチルイソ尿素硫酸塩を
得る方法が好適に採用できる。この場合硫酸は、シアナ
ミド１モルに対して２当量以上用いるのがよく、２〜２
．５当量用いるのがより好ましい。Generally, the reaction (9) above is extremely fast, and the reaction (10) above is extremely fast.
The reaction is slow. Therefore, when trying to obtain a sulfate of O-methylisourea, first, use equimolar sulfuric acid to the cyanamide to convert all the cyanamide into a hydrogensulfate of O-methylisourea, and then, as shown in the following formula, A compound that acts as an alkali in this reaction system (hereinafter referred to as
A method of obtaining the target O-methylisourea sulfate by carrying out an addition reaction with a compound (sometimes simply referred to as an alkaline compound) can be suitably employed. In this case, sulfuric acid is preferably used in an amount of 2 or more equivalents per mole of cyanamide, and 2 to 2 equivalents are used per mole of cyanamide.
．． More preferably, 5 equivalents are used.
（但し、ＢＯＨはアルカリを表す）
アルカリ性化合物の使用量は、一般にシアナミド１モル
に対しての酸の必要量である１当量を超えて添加された
硫酸の過剰分を中和するに要する量であればよい。(However, BOH represents alkali) The amount of alkaline compound used is generally the amount required to neutralize the excess amount of sulfuric acid added in excess of 1 equivalent, which is the required amount of acid for 1 mole of cyanamide. Good to have.
なお、上記アルカリ性化合物を添加するのに先立ち、適
宜の量の水を加えて上記硫酸水素塩を溶解させ、均一溶
液とすることができる。このように均一溶液とすること
によって、上記（１１）の反応をスムースに進行させる
ことができる。Note that, prior to adding the alkaline compound, an appropriate amount of water can be added to dissolve the hydrogen sulfate to form a homogeneous solution. By forming a homogeneous solution in this way, the reaction (11) above can proceed smoothly.
前記のアルカリ性化合物としては、例えば、炭酸カルシ
ウム、水酸化カルシウム等のアルカリ土類金属の炭酸塩
もしくは水酸化物；例えば、炭酸ナトリウム、炭酸水素
ナトリウム、水酸化ナトリウム、水酸化カリウム等のア
ルカリ金属の炭酸塩、炭酸水素塩もしくは水酸化物；陰
イオン交換樹脂：等を挙げることができる。これらのう
ち、入手の容易性、取り扱いの容易さ、価格の低廉さ等
の理由から炭酸カルシウムの使用が好ましい。Examples of the alkaline compounds include carbonates or hydroxides of alkaline earth metals such as calcium carbonate and calcium hydroxide; Carbonates, hydrogen carbonates, or hydroxides; anion exchange resins; and the like. Among these, calcium carbonate is preferably used because of its ease of availability, ease of handling, and low price.
本発明の製法によれば、出発原料として、製造上及び貯
蔵上多くの問題を抱えているシアナミド結晶などのシア
ナミド単離体を用いず、メタノール含有有機液体中で、
石灰窒素に炭酸ガスを反応させることによりシアナミド
を溶液として遊離させ、この溶液にそのまま硫酸などの
酸を添加反応させるだけでよいので、高収率で高純度の
Ｏ−メチルイソ尿素塩を工業的シこ、安全且つ容易に製
造することが可能になる。According to the production method of the present invention, cyanamide isolates such as cyanamide crystals, which have many problems in production and storage, are not used as a starting material, and cyanamide is produced in a methanol-containing organic liquid.
Cyanamide is liberated as a solution by reacting carbon dioxide gas with lime nitrogen, and it is only necessary to add an acid such as sulfuric acid to this solution and react, so it is possible to produce O-methylisourea salt with high yield and high purity in an industrial system. This makes it possible to manufacture safely and easily.
以下に実施例により本発明を更に具体的に説明する。 The present invention will be explained in more detail below with reference to Examples.
実施例１
１／：の攪拌装置及び還流冷却管付けた４つロフラスコ
に、メタノール６００ｍ４ （４７５ｇ） （純度９９
．５重量％以上、水含量０．１重量％以下）及び石灰窒
素１００ｇ［窒素含有量２３．６重量％（カルシウムシ
アナミドとしての窒素含有量２３．６重量％）；粒度２
００メツシュ通過６５重量％］を仕込み、攪拌によりス
ラリー状に分散させた。次いで攪拌下、約１０℃に保ち
ながら約５時間で８８ｇの炭酸ガス（純度９９．９９重
量％）を導入し、そのま）の温度で１時間攪拌しながら
反応させた。反応終了後、メタノール不溶分を濾別した
。得られた濾液（メタノール溶液）中の水含有量はＧＣ
分析（ＴＣＤ法）により１゜８重量％であった。メタノ
ール不溶分は、反応に用いたと同様のメタノール１５０
１ （１１９ｇ）で洗浄し、洗浄液を濾液に合せた。溶
存する炭酸ガスを除去するため、濾液は減圧下、３０℃
以下の温度で約半量となるまで濃縮し、２５０ｇの濃縮
濾液、すなわち、シアナミドのメタノール溶液を得た。Example 1 600 m4 (475 g) of methanol (purity 99
．． 5% by weight or more, water content 0.1% by weight or less) and 100 g of lime nitrogen [nitrogen content 23.6% by weight (nitrogen content as calcium cyanamide 23.6% by weight); particle size 2
65% by weight] was charged and dispersed into a slurry by stirring. Next, 88 g of carbon dioxide gas (purity 99.99% by weight) was introduced over a period of about 5 hours while stirring and maintaining the temperature at about 10° C., and the mixture was allowed to react at that temperature for 1 hour while stirring. After the reaction was completed, methanol-insoluble matter was filtered off. The water content in the obtained filtrate (methanol solution) was determined by GC
Analysis (TCD method) showed that it was 1.8% by weight. The methanol insoluble matter is the same methanol 150 used in the reaction.
1 (119 g), and the washing liquid was combined with the filtrate. To remove dissolved carbon dioxide, the filtrate was heated at 30°C under reduced pressure.
The mixture was concentrated to about half its volume at the following temperature to obtain 250 g of a concentrated filtrate, that is, a methanol solution of cyanamide.
該メタノール溶液中のシアナミドおよび副生ジシアンジ
アミドの含有量は、液体クロマトグラフィー（以下、Ｌ
Ｃと略称することがある）分析により、それぞれ、１３
．９重量％および０．０５４重量％であり、原料石灰窒
素中のカルシウムシアナミドに対するシアナミドの生成
収率は９８．２％、ジシアンジアミドの生成率は０．３
８％であった。The content of cyanamide and by-product dicyandiamide in the methanol solution was determined by liquid chromatography (hereinafter referred to as L
(sometimes abbreviated as C) analysis revealed that 13
．． 9% by weight and 0.054% by weight, the production yield of cyanamide with respect to calcium cyanamide in the raw lime nitrogen is 98.2%, and the production rate of dicyandiamide is 0.3.
It was 8%.
上記メタノール溶液には、８５重量％リン酸少量を加え
て攪拌し、生じた不溶分を濾別した後、該溶液の７１度
を５〜１０℃に保ちながら、濃硫酸９０．５ｇ（濃度９
５重量％ニジアナミド１モルに対して２．２当量）を３
時間で添加し、そのままの温度で２．５時間保持した。A small amount of 85% by weight phosphoric acid was added to the above methanol solution, stirred, and the resulting insoluble matter was filtered out.While maintaining the solution at 71°C at 5-10°C, 90.5g of concentrated sulfuric acid (concentration 9
2.2 equivalents per mole of 5% by weight nidianamide) at 3
The mixture was added at a certain time and kept at that temperature for 2.5 hours.
次いで脱イオン水２００ｍ Ｉ：を加えて析出している
○−メチルイソ尿素の硫酸水素塩スラリーを溶解させて
０−メチルイソ尿素の硫酸水素塩のメタノール−水均−
溶液５４１ｇを得た。この均一溶液をＬＣ分析したとこ
ろ、０−メチルイソ尿素の硫酸水素塩の含有量は２４．
５重量％であり、副生尿素は０、３６５重量％であって
、原料石灰窒素中のシアナミドに対する０−メチルイソ
尿素の生成収率は９１．４％であった。Next, 200 m of deionized water was added to dissolve the precipitated ○-methylisourea hydrogen sulfate slurry, and the 0-methylisourea hydrogen sulfate was dissolved in methanol-water.
541 g of solution was obtained. When this homogeneous solution was analyzed by LC, the content of hydrogen sulfate of 0-methylisourea was found to be 24.
5% by weight, by-product urea was 0.365% by weight, and the production yield of 0-methylisourea based on cyanamide in the raw lime nitrogen was 91.4%.
次に得られた０−メチルイソ尿素の硫酸水素塩のメタノ
ール−水均−溶液に、攪拌しながら炭酸カルシウム粉末
（純度９８重量％）をｐＨが３〜５となるまで添加し、
更に１時間攪拌を継続した。沈澱した硫酸カルシウムは
濾別して１５０ａ４’の脱イオン水で洗浄し、洗浄液は
濾液に合わせた。Next, calcium carbonate powder (purity 98% by weight) was added to the obtained methanol-water solution of hydrogen sulfate of 0-methylisourea while stirring until the pH became 3 to 5.
Stirring was continued for an additional hour. The precipitated calcium sulfate was filtered off and washed with 150a4' of deionized water, and the washings were combined with the filtrate.
かくして得られたＯ−メチルイソ尿素硫酸塩の溶液を減
圧下、５０℃以下の温度でａ縮乾固し、１００ｍ４のメ
タノールを加えて室温まで冷却し、生成したＯ−メチル
イソ尿素硫酸塩の結晶を濾別し、次いで６０℃の温度で
減圧乾燥した。得られたＯ−メチルイソ尿素硫酸塩結晶
は８５．０ｇ（原料石灰窒素中のシアナミドに対するＯ
−メチルイソ尿素硫酸塩の生成収率８２．４％）であっ
た。The solution of O-methylisourea sulfate thus obtained was condensed to dryness under reduced pressure at a temperature of 50°C or less, and 100 m4 of methanol was added and cooled to room temperature to obtain crystals of O-methylisourea sulfate. It was filtered and then dried under reduced pressure at a temperature of 60°C. The obtained O-methylisourea sulfate crystals weighed 85.0 g (O
- Production yield of methyl isourea sulfate was 82.4%).
分析したところ、次のとおりであった。The analysis revealed the following.
純度 ９９，２重量％尿素
０．５重量％水分
ｏ、ｏｓｉｉ量％実施例２
実施例１と同様の装置を用いて同様にして得たシアナミ
ドのメタノール溶液２５０ｇに、同様に８５重量％リン
酸少景を加えて攪拌し、生じた不溶分を濾別した後、該
溶液の温度を５〜１０℃に保ちながら、塩化水素ガス７
２ｇ（純度９９．９重量％ニジアナミド１モルに対して
２当量）を４時間で添加し、そのままの温度で２４時間
保持した。生成した０−メチルイソ尿素塩酸塩の結晶を
濾別し、次いで６０″Ｃの温度で減圧乾燥した。得られ
た０−メチルイソ尿素塩酸塩結晶は６６．０ｇ＜原料石
灰窒素中のシアナミドに対する０−メチルイソ尿素塩酸
塩の生成収率６４．５％）であった。また、濾液は減圧
下、３０℃以下の温度で濃縮乾固し、次いで３０ｍ ｌ
のメタノールを加えて室温まで冷却し、生成した結晶を
濾別することによりさらに２０．０ｇ（原料石灰窒素中
のシアナミドに対するＯ−メチルイン尿素塩酸塩の生成
収率１９．５％）の０−メチルイソ尿素塩酸塩を得るこ
とができた。原料石灰窒素中のシアナミドに対するＯ−
メチルイソ尿素塩酸塩の合計の生成収率は８４％であっ
た。Purity 99.2% by weight urea
0.5% water by weight
o, osii amount% Example 2 To 250 g of a methanol solution of cyanamide obtained in the same manner as in Example 1, 85% by weight of phosphoric acid was added and stirred, and the resulting insoluble matter was removed. After filtering, while keeping the temperature of the solution at 5 to 10°C, hydrogen chloride gas
2 g (2 equivalents per mole of Nidianamide with a purity of 99.9% by weight) was added over 4 hours, and the temperature was maintained for 24 hours. The produced crystals of 0-methylisourea hydrochloride were separated by filtration and then dried under reduced pressure at a temperature of 60''C. The production yield of methyl isourea hydrochloride was 64.5%).The filtrate was concentrated to dryness under reduced pressure at a temperature below 30°C, and then 30ml
of methanol was added and cooled to room temperature, and the formed crystals were filtered to obtain an additional 20.0 g (19.5% production yield of O-methylinurea hydrochloride based on cyanamide in the raw lime nitrogen) of 0-methylisomer. We were able to obtain urea hydrochloride. O- for cyanamide in raw lime nitrogen
The total production yield of methyl isourea hydrochloride was 84%.
分析したところ、次のとおりであった。The analysis revealed the following.
純度 ９９．９重量％ 尿素 Ｏ５重量％ 水分 ０．１重量％purity 99.9% by weight urea O5 weight% moisture 0.1% by weight
Claims (1)
中に分散させ、得られた分散液の中に炭酸ガスを導入す
ることにより該有機液体中のシアナミド溶液を生成させ
、次いで該シアナミド溶液に酸を添加することを特徴と
するＯ−メチルイソ尿素塩の製法。(1) Lime nitrogen is dispersed in an organic liquid containing methanol, carbon dioxide gas is introduced into the resulting dispersion to generate a cyanamide solution in the organic liquid, and then the cyanamide solution A method for producing O-methyl isourea salt, which comprises adding an acid to.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1296286A JP2748170B2 (en) | 1989-11-16 | 1989-11-16 | Process for producing O-methylisourea salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1296286A JP2748170B2 (en) | 1989-11-16 | 1989-11-16 | Process for producing O-methylisourea salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03157358A true JPH03157358A (en) | 1991-07-05 |
| JP2748170B2 JP2748170B2 (en) | 1998-05-06 |
Family
ID=17831596
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1296286A Expired - Fee Related JP2748170B2 (en) | 1989-11-16 | 1989-11-16 | Process for producing O-methylisourea salt |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2748170B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999033809A1 (en) * | 1997-12-24 | 1999-07-08 | Takeda Chemical Industries, Ltd. | Method for producing isoureas |
| WO2007105793A1 (en) | 2006-03-16 | 2007-09-20 | Sumitomo Chemical Company, Limited | Method for nitrating isourea |
| CN103896813A (en) * | 2014-04-10 | 2014-07-02 | 宁夏宝马化工集团有限公司 | High-purity dicyandiamide production process |
| WO2021206132A1 (en) * | 2020-04-09 | 2021-10-14 | 三井化学アグロ株式会社 | Improved method for producing o-methylisourea sulfate |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3670022A (en) | 1969-11-26 | 1972-06-13 | American Cyanamid Co | Continuous high temperature process for o-methylpseudourea hydrochloride |
| DE2358904A1 (en) | 1973-11-27 | 1975-06-05 | Sueddeutsche Kalkstickstoff | O-methyl-isourea sulphate prepn. in two stages - from cyanamide, sulphuric acid and methanol |
| US3931316A (en) | 1974-08-10 | 1976-01-06 | Suddeutsche Kalkstickstoff-Werke Ag | Method of preparing O-methyl-isourea hydrogen sulfate and O-methyl-isourea sulfate from cyanamide |
-
1989
- 1989-11-16 JP JP1296286A patent/JP2748170B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999033809A1 (en) * | 1997-12-24 | 1999-07-08 | Takeda Chemical Industries, Ltd. | Method for producing isoureas |
| US6265582B1 (en) | 1997-12-24 | 2001-07-24 | Takeda Chemical Industries, Ltd. | Method for producing isoureas |
| WO2007105793A1 (en) | 2006-03-16 | 2007-09-20 | Sumitomo Chemical Company, Limited | Method for nitrating isourea |
| CN103896813A (en) * | 2014-04-10 | 2014-07-02 | 宁夏宝马化工集团有限公司 | High-purity dicyandiamide production process |
| CN103896813B (en) * | 2014-04-10 | 2015-09-30 | 宁夏宝马化工集团有限公司 | Dyhard RU 100 production technique |
| WO2021206132A1 (en) * | 2020-04-09 | 2021-10-14 | 三井化学アグロ株式会社 | Improved method for producing o-methylisourea sulfate |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2748170B2 (en) | 1998-05-06 |
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