JPS6159294B2 - - Google Patents
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- Publication number
- JPS6159294B2 JPS6159294B2 JP53128851A JP12885178A JPS6159294B2 JP S6159294 B2 JPS6159294 B2 JP S6159294B2 JP 53128851 A JP53128851 A JP 53128851A JP 12885178 A JP12885178 A JP 12885178A JP S6159294 B2 JPS6159294 B2 JP S6159294B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- water
- emulsifier
- hydrate
- production rate
- 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
Links
- 238000004519 manufacturing process Methods 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 22
- -1 polyoxyethylene Polymers 0.000 claims description 17
- 150000004677 hydrates Chemical class 0.000 claims description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 8
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 claims description 6
- XWCDCDSDNJVCLO-UHFFFAOYSA-N Chlorofluoromethane Chemical compound FCCl XWCDCDSDNJVCLO-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 4
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 3
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 claims description 3
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 claims description 3
- UMNKXPULIDJLSU-UHFFFAOYSA-N dichlorofluoromethane Chemical compound FC(Cl)Cl UMNKXPULIDJLSU-UHFFFAOYSA-N 0.000 claims description 3
- 229940099364 dichlorofluoromethane Drugs 0.000 claims description 3
- 239000002736 nonionic surfactant Substances 0.000 claims description 3
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 claims description 3
- 229940029284 trichlorofluoromethane Drugs 0.000 claims description 3
- 239000004338 Dichlorodifluoromethane Substances 0.000 claims description 2
- 235000019404 dichlorodifluoromethane Nutrition 0.000 claims description 2
- NMJORVOYSJLJGU-UHFFFAOYSA-N methane clathrate Chemical compound C.C.C.C.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O NMJORVOYSJLJGU-UHFFFAOYSA-N 0.000 claims 1
- 239000003995 emulsifying agent Substances 0.000 description 27
- 230000000694 effects Effects 0.000 description 10
- 238000003756 stirring Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 6
- 238000009775 high-speed stirring Methods 0.000 description 5
- 238000007711 solidification Methods 0.000 description 5
- 230000008023 solidification Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 125000006353 oxyethylene group Chemical group 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229920006197 POE laurate Polymers 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical class FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Colloid Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
この発明は気体水化物の製造法に関するもので
ある。
気体水化物は海水の淡水化、汚水の再生、ジユ
ース類の濃縮、炭化水素異性体の分離、冷房用蓄
熱材など広範囲に利用されている。
周知のように気体水化物には型、型などが
あり、それぞれ式Ｍ・５3/4H2O、Ｍ・17H2Oで
表わされる。ここにＭはゲスト分子と呼ばれる。
一般には有機物質でフロン系化合物を除くと、分
子量100以下の軽い物質であり、水にはほとんど
溶解しないものが多い。たとえばメタン、エタ
ン、酸化エチレンなどは型気体水化物を、また
塩化エチル、トリクロルフルオルメタン
（R11）、ジクロルフルオルメタン（R21）などは
型気体水化物を生成する。
気体水化物を効率よく生成させるためには、こ
れらゲスト分子と水とをできる限り効率よく接触
させねばならない。したがつて、実際には気体水
化物の製造に当つては、ゲスト分子と水とを効率
よく接触させるために、液体状態での高速度な撹
拌や、両物質を霧状にして混合するなどの手段が
とられる。例えば、撹拌速度を大きくすればする
ほど気体水化物の生成速度が大きくなることはよ
く知られている。
ところが、気体水化物は氷に似た固体であつ
て、撹拌によつて生じた微結晶は液体に分散して
スラリー状となり、気体水化物が生成すればする
ほど、その系の粘性はますます大きくなり、高速
度の撹拌がますます困難なものになつてくる。こ
のような撹拌機能の低下は、ゲスト分子と水との
接触の機会を必然的に減少させることから、気体
水化物の単位時間あたりの生成量も減少すること
になる結果、生成量は時間の経過につれて頭打ち
傾向になる。また、気体水化物がある程度生成し
たにもかかわらず、高速撹拌を強引に続けると、
撹拌装置の破損をもたらすことになる。
従来の製造法は上記のようにゲスト分子に水を
加えるのみであつた。この従来の製造法による気
体水化物の生成率をR11（CCl3F）水化物の製造
の場合について第１図に示す。図中、横軸はR11
１モルに対する水のモル数、縦軸は重量％による
R11水化物生成率を示す。これは、通常の撹拌装
置（撹拌速度は数百rpm）によるR11−水系の場
合（０℃に冷却）の実測結果である。上記第１図
より明らかなように、R11不足組成（2OH2O）か
らR11過剰組成（14H2O）までR11の濃度を変化
させても、気体水化物の生成率はそれほど変わら
ず、R11濃度が小さくなると生成率はやや減少す
る傾向となる。なお、この系を24時間冷却して
も、生成率はわずか２〜３重量％しか増加しな
い。従来の方法では、次のような問題点があつ
た。
(1) 気体水化物の生成が容易に開始しない。すな
わち、核生成が困難なため、過冷却が避け難
い。
(2) 生成速度が小さいため、単位時間当りの生成
量が少なく、実用的に要求される生成速度に達
しない。
(3) 生成率に上限値があり、その値は約50重量％
であること。
この発明は、上記のような従来の方法の欠点を
除去するためになされたもので、気体水化物製造
時に、あらかじめ、水にポリオキシエチレン系非
イオン系界面活性剤（以後、単に乳化剤と呼ぶ）
を所定量添加しておくことにより（第１の発
明）、また上記界面活性剤とともにフランなどの
特定の化合物を添加しておくことにより（第２の
発明）生成速度が大きくて冷却速度に追従すると
共に、あまり高速の撹拌手段を用いることなく、
生成率の上限値を大巾に向上させうる気体水化物
の製造法を提供するものである。
即ち第１の発明は、水に対して乳化剤を0.5〜
５重量％含む水とクロルフルオルメタン系ゲスト
分子とを接触させることを特徴とする気体水化物
の製造法に関するものであり、第２の発明は水に
対して乳化剤0.5〜５重量％と、水に対して0.5〜
８重量％のテトラハイドロフラン、フラン、メチ
ルフランおよびメチルテトラハイドロフランより
なる群から選ばれた少なくとも一つの化合物とを
含む水とクロルフルオルメタン系ゲスト分子とを
接触させることを特徴とする気体水化物の製造法
に関するものである。
本発明に用いられる上記乳化剤としては、例え
ばポリオキシエチレン系アルキルフエノールエー
テルでアルキル基がノニル基あるいはオクチル基
よりなり、HLB指数５〜16のもの、あるいはポ
リオキシエチレン系アルキルエーテルでアルキル
基がラウリル基あるいはオレイル基あるいはトリ
デシル基あるいはセチル基あるいはステアリル基
よりなり、HLB指数が５〜16のもの、あるいは
ポリオキシエチレン系のアルキルエステルでアル
キル基が、ラウリル基あるいはオレイル基あるい
はステアリル基よりなり、HLB指数５〜16のも
の、あるいはオキシエチレンとオキシプロピレン
のブロツク共重合体でオキシエチレン基を25重量
％以上含むものなどが挙げられる。これらは単独
で、もしくは２種以上混合して用いることができ
る。
上記乳化剤の水に対する添加量は0.5重量％〜
５重量％である。0.5重量％未満では効果の発現
が不十分であり、５重量％こえると気体水化物の
生成速度が低下するようになり、また不経済であ
る。
上記特定のフラン化合物を上記乳化剤に加えて
配合する第２の発明では、固化開始までに要する
時間が大巾に短縮されるという顕著な効果が重畳
される。なおこの場合の上記特定のフラン化合物
の水に対する添加量は0.5〜８重量％である。こ
の量が0.5重量％未満では効果の発現が不十分で
あり、一方８重量％こえると固化開始までに要す
る時間が更に短縮されるということはないので、
無駄を生じることになる。
また、上記クロルフルオルメタン系ゲスト分子
としては、トリクロルフルオルメタン（R11）、
ジクロルフルオルメタン（R21）、モノクロルジ
フルオルメタン（R22）およびジクロルジフルオ
ルメタン（R12）が用いられる。これらは単独で
もしくは任意の二種以上を混合して用いることが
できる。
なおこれらのゲスト分子と上記特定の化合物を
含む水とを接触させるに際しては公知の従来技術
が適宜用いられる。
以下、一実施例について、この発明をさらに具
体的に説明する。
第２図はR11水化物を製造した場合における乳
化剤濃度と生成率の関係を示す。図において横軸
は水に対して添加した乳化剤の重量％、縦軸は重
量％による乳化剤を含む水に対するR11水化物生
成率（乳化剤はR11水化物になりえないため該生
成率が100％になることはない）生成率である。
この実験は第１図の場合と同じ装置を用い、同一
条件下で行なつたものでありR11・17H2Oの組成
液に乳化剤を加えたものを試料とした。
図示の乳化剤濃度はゲスト分子１分子に対して
水17分子（17H2O）の場合の水に対する添加濃度
である。ここで用いた乳化剤はポリオキシエチレ
ンノニルフエニルエーテル
This invention relates to a method for producing gaseous hydrates. Gaseous hydrates are used in a wide range of applications, including desalination of seawater, recycling of wastewater, concentration of youths, separation of hydrocarbon isomers, and heat storage materials for air conditioning. As is well known, there are different types of gas hydrates, which are represented by the formulas M.53/4H 2 O and M.17H 2 O, respectively. Here M is called a guest molecule.
In general, organic substances, excluding fluorocarbon compounds, are light substances with a molecular weight of less than 100, and many are hardly soluble in water. For example, methane, ethane, ethylene oxide, etc. produce type gas hydrates, and ethyl chloride, trichlorofluoromethane (R11), dichlorofluoromethane (R21), etc. produce type gas hydrates. In order to efficiently generate gaseous hydrate, these guest molecules must be brought into contact with water as efficiently as possible. Therefore, in actual production of gaseous hydrates, in order to bring guest molecules into contact with water efficiently, it is necessary to use high-speed stirring in the liquid state, or to mix both substances in the form of a mist. measures will be taken. For example, it is well known that the higher the stirring speed, the faster the rate of gaseous hydrate formation. However, gaseous hydrate is a solid similar to ice, and the microcrystals produced by stirring are dispersed in the liquid to form a slurry, and the more gaseous hydrate is produced, the more viscous the system becomes. As the size increases, high-speed stirring becomes increasingly difficult. This reduction in the stirring function inevitably reduces the opportunity for guest molecules to come into contact with water, and as a result, the amount of gaseous hydrate produced per unit time also decreases. As time passes, it tends to plateau. In addition, even though a certain amount of gaseous hydrate has been generated, if high-speed stirring is continued forcibly,
This will result in damage to the stirring device. The conventional production method simply added water to the guest molecules as described above. The production rate of gaseous hydrate by this conventional production method is shown in FIG. 1 for the production of R11 (CCl 3 F) hydrate. In the figure, the horizontal axis is R11
Number of moles of water per mole, vertical axis is by weight%
The R11 hydrate production rate is shown. This is an actual measurement result in the case of R11-water system (cooled to 0° C.) using a normal stirring device (stirring speed is several hundred rpm). As is clear from Figure 1 above, even if the R11 concentration is changed from an R11-deficient composition (2OH 2 O) to an R11-excessive composition (14H 2 O), the production rate of gaseous hydrate does not change much, and the R11 concentration When , the production rate tends to decrease slightly. Note that even if the system is cooled for 24 hours, the production rate increases by only 2-3% by weight. The conventional method has the following problems. (1) Formation of gaseous hydrates does not start easily. That is, since nucleation is difficult, supercooling is difficult to avoid. (2) Since the production rate is low, the amount of production per unit time is small and does not reach the production rate required for practical purposes. (3) There is an upper limit to the production rate, which is approximately 50% by weight.
To be. This invention was made in order to eliminate the drawbacks of the conventional method as described above, and when producing a gaseous hydrate, a polyoxyethylene nonionic surfactant (hereinafter simply referred to as an emulsifier) is added to water in advance. )
By adding a predetermined amount of (first invention), and by adding a specific compound such as furan together with the above surfactant (second invention), the production rate is high and follows the cooling rate. At the same time, without using too high-speed stirring means,
The present invention provides a method for producing gaseous hydrates that can greatly improve the upper limit of the production rate. That is, in the first invention, the emulsifier is added to water from 0.5 to
The second invention relates to a method for producing a gaseous hydrate characterized by contacting water containing 5% by weight with chlorofluoromethane guest molecules, and the second invention relates to a method for producing a gaseous hydrate characterized by contacting water containing 0.5 to 5% by weight of an emulsifier with respect to water, 0.5~ for water
A gas characterized by contacting water containing 8% by weight of at least one compound selected from the group consisting of tetrahydrofuran, furan, methylfuran and methyltetrahydrofuran with a chlorofluoromethane guest molecule. It relates to a method for producing hydrates. Examples of the emulsifier used in the present invention include polyoxyethylene-based alkyl phenol ethers in which the alkyl group consists of a nonyl group or octyl group and an HLB index of 5 to 16, or polyoxyethylene-based alkyl ethers in which the alkyl group consists of lauryl groups. or an oleyl group, a tridecyl group, a cetyl group, or a stearyl group, and has an HLB index of 5 to 16, or a polyoxyethylene alkyl ester whose alkyl group is a lauryl group, an oleyl group, or a stearyl group, and has an HLB index of 5 to 16. Examples include those having an index of 5 to 16, or block copolymers of oxyethylene and oxypropylene containing 25% by weight or more of oxyethylene groups. These can be used alone or in combination of two or more. The amount of the above emulsifier added to water is 0.5% by weight or more.
It is 5% by weight. If it is less than 0.5% by weight, the effect will not be sufficiently expressed, and if it exceeds 5% by weight, the production rate of gaseous hydrate will decrease and it will be uneconomical. In the second aspect of the invention, in which the above-mentioned specific furan compound is added to the above-mentioned emulsifier, the remarkable effect of greatly shortening the time required to start solidification is superimposed. In this case, the amount of the specific furan compound added to water is 0.5 to 8% by weight. If this amount is less than 0.5% by weight, the effect will not be sufficiently expressed, while if it exceeds 8% by weight, the time required to start solidification will not be further shortened.
This will result in waste. In addition, the above-mentioned chlorofluoromethane-based guest molecules include trichlorofluoromethane (R11),
Dichlorofluoromethane (R21), monochlorodifluoromethane (R22) and dichlorodifluoromethane (R12) are used. These can be used alone or in a mixture of two or more. Note that known conventional techniques can be used as appropriate when bringing these guest molecules into contact with water containing the above-mentioned specific compound. Hereinafter, the present invention will be described in more detail with reference to one embodiment. Figure 2 shows the relationship between emulsifier concentration and production rate when R11 hydrate is produced. In the figure, the horizontal axis is the weight % of the emulsifier added to water, and the vertical axis is the R11 hydrate production rate in water containing the emulsifier (the production rate is 100% because the emulsifier cannot turn into R11 hydrate). ) is the production rate.
This experiment was carried out using the same apparatus and under the same conditions as in the case of FIG. 1, and the sample was a composition of R11.17H 2 O to which an emulsifier was added. The emulsifier concentration shown in the figure is the concentration added to water in the case of 17 water molecules (17H 2 O) per molecule of guest molecule. The emulsifier used here is polyoxyethylene nonyl phenyl ether.
【式】でｎが８、
HLB指数12.3のものである。なおHLB指数の算出
はすべてGriffin（1954）の方法による。図では
乳化剤濃度0.8重量％では生成率に対してはあま
り顕著な効果が現われていないが、R11水化物が
生成するまでの時間は無添加の場合に比べて大巾
に短縮されることがわかる。乳化剤濃度２重量％
では生成率、生成速度ともに、ほぼ最高値が得ら
れ、無添加の場合に比して、水化物の生成率は約
２倍、また生成速度は約3.6倍（無添加の場合の
生成速度は約0.5wt％／分である）に上昇する。
なお、4.2重量％添加したものでは２重量％添加
加したものに比して、生成率はそれほど低下しな
いのに反して、生成速度はかなり低下するといえ
る。経済的には、できる限り少量の添加で最大の
効果を得る必要があることから、実用的な乳化剤
の添加量は0.5〜５重量％の範囲内にあることが
適当である。なお、特に好ましい乳化剤を列挙す
ればポリオキシエチレンオレイルエーテル
（C17H32−Ｏ−（C2H4O）o−Ｈ）でｎ＝５、HLB指
数9.0；ポリオキシエチレンラウリルエーテル
（C11H23−Ｏ−（C2H4O）o−Ｈ）でｎ＝５、HLB指
数10.8；ポリオキシエチレン・ラウレート（HLB
指数10.5）；ポリオキシエチレン・オレエート
（HLB指数9.0）などのエステル系のほか、オキシ
エチレン・オキシプロピレンのブロツクポリマー
（分子量約3000、オキシエチレン基約40重量％）
などが挙げられる。また、これらよりも効果はや
や劣るとはいえ無添加のものと比較すれば明らか
に効果を有するといえるものには、たとえばポリ
オキシエチレンノニルフエニルエーテルでは
HLB指数8.9〜16.0のものなどが挙げられる。
第３図は、ポリオキシエチレンラウレート
（HLB指数10.8）を２重量％加えたものと、無添
加の場合の固化時の発熱温度の時間変化を示す。
乳化剤を添加したものは、融点に近い発熱温度が
長時間続くことがわかる。
第４図は水に乳化剤（ポリオキシエチレンノニ
ルフエニルエーテル、HLB指数12.3）2.0重量％
加えたものと、これにさらにテトラハイドロフラ
ン（THF）4.0重量％を加えたものとを比較して
示す特性図である。なお、いずれもR11水化物に
ついてのものである。第４図から明らかなように
乳化剤とTHFとを添加したものは０℃に冷却し
た場合、固化開始までに要する時間は１分以内で
あるのに対し、THFを添加しないものは、通常
50分程度も必要であり、THFの添加による核生
成への効果が明瞭に認められる。
上記実施例から明らかなように乳化剤とTHF
とは相互補完的な作用を有しており、これら双方
の併用によりR11・17H2Oが有する欠点である生
成速度の遅さと固化し難さの両方を同時に解決す
ることができる。
なお上記THFの他にフラン、メチルフラン、
メチルテトラハイドロフランも同様の効果を奏す
ることが認められた。
以上のように、この発明によれば次のような効
果がえられる。
(1) 水化物の生成速度は乳化剤無添加の場合に比
べて３倍以上大きくなる。
(2) 水化物の生成率も約２倍に向上させることが
でき、75重量％以上にできることから、材料の
利用効率が高くなり、無駄分が少なくなる。
(3) 高速度の撹拌装置、あるいは強力な撹拌装置
を必要とせず経済的である。上記(1)、(2)項にあ
げた効果があるので、水化物生成開始後、数分
して撹拌を停止しても常に生成を得ることがで
きる。
(4) 水化物の生成速度が大きく、融点に近い発熱
が持続されるので、系から奪われる熱量に相当
する水化物が生成することになり、熱経済的に
も損失が無く経済的となる。In [Formula], n is 8 and the HLB index is 12.3. All HLB index calculations are based on the method of Griffin (1954). The figure shows that an emulsifier concentration of 0.8% by weight does not have a very significant effect on the production rate, but the time it takes to produce R11 hydrate is significantly shortened compared to when no additive is used. . Emulsifier concentration 2% by weight
Almost the highest values were obtained for both the production rate and the production rate, and the hydrate production rate was about twice that of the case without additives, and the production rate was about 3.6 times (the production rate in the case of no additives was (approximately 0.5 wt%/min).
It should be noted that when 4.2% by weight is added, the production rate is not so much lower than when 2% by weight is added, but it can be said that the production rate is considerably lower. Economically, it is necessary to obtain the maximum effect by adding as little as possible, so the practical amount of the emulsifier to be added is suitably within the range of 0.5 to 5% by weight. Particularly preferred emulsifiers include polyoxyethylene oleyl ether (C 17 H 32 -O-(C 2 H 4 O) o -H), n=5, HLB index 9.0; polyoxyethylene lauryl ether (C 11 H23 -O-( C2H4O ) o -H), n=5, HLB index 10.8; polyoxyethylene laurate ( HLB
Index 10.5); In addition to esters such as polyoxyethylene oleate (HLB index 9.0), block polymers of oxyethylene and oxypropylene (molecular weight approximately 3000, oxyethylene group approximately 40% by weight)
Examples include. In addition, although the effect is slightly inferior to these, there are substances that can be said to be clearly effective when compared with additive-free substances, such as polyoxyethylene nonyl phenyl ether.
Examples include those with an HLB index of 8.9 to 16.0. FIG. 3 shows the time change in exothermic temperature during solidification for the case where 2% by weight of polyoxyethylene laurate (HLB index 10.8) was added and when no addition was made.
It can be seen that the exothermic temperature close to the melting point continues for a long time when an emulsifier is added. Figure 4 shows 2.0% by weight of emulsifier (polyoxyethylene nonyl phenyl ether, HLB index 12.3) in water.
FIG. 2 is a characteristic diagram showing a comparison between a product with the addition of 4.0% by weight of tetrahydrofuran (THF) and a product with 4.0% by weight of tetrahydrofuran (THF) added thereto. Note that all of these are for R11 hydrate. As is clear from Figure 4, when the emulsifier and THF are added, it takes less than 1 minute to start solidifying when cooled to 0°C, whereas the emulsifier without THF usually starts solidifying within 1 minute.
It takes about 50 minutes, and the effect of adding THF on nucleation is clearly recognized. As is clear from the above examples, emulsifier and THF
and have mutually complementary effects, and by using both in combination, it is possible to simultaneously solve both of the drawbacks of R11.17H 2 O, such as slow production rate and difficulty in solidifying. In addition to the above THF, furan, methylfuran,
Methyltetrahydrofuran was also found to have similar effects. As described above, according to the present invention, the following effects can be obtained. (1) The hydrate formation rate is more than three times higher than when no emulsifier is added. (2) The production rate of hydrates can be approximately doubled to over 75% by weight, resulting in higher material utilization efficiency and less waste. (3) It is economical as it does not require a high-speed stirring device or a powerful stirring device. Because of the effects listed in items (1) and (2) above, hydrate production can always be obtained even if stirring is stopped several minutes after the start of hydrate production. (4) Since the rate of hydrate generation is high and heat generation close to the melting point is sustained, hydrate equivalent to the amount of heat removed from the system is generated, making it economical with no thermoeconomic loss. .
第１図は従来の乳化剤無添加の場合における
R11・１モルに対する水のモル数が変化した場合
の気体水化物の生成率を示す特性図、第２図はこ
の発明の一実施例による製造法の乳化剤添加の場
合のR11・17H2Oの生成率、生成速度を示す特性
図、第３図はこの発明の他の実施例による製造法
の乳化剤添加の場合および無添加の場合の固化時
の発熱温度を示す特性図である。第４図は乳化剤
のみの場合と乳化剤とTHFとを加えた場合の固
化開始までの時間と温度との関係を示す特性図で
ある。
Figure 1 shows the conventional case with no emulsifier added.
A characteristic diagram showing the production rate of gaseous hydrate when the number of moles of water relative to 1 mole of R11 changes. Figure 2 is a characteristic diagram showing the production rate of gaseous hydrate when the number of moles of water relative to 1 mole of R11 changes. FIG. 3 is a characteristic diagram showing the production rate and production speed, and FIG. 3 is a characteristic diagram showing the exothermic temperature during solidification in the production method according to another embodiment of the present invention with and without the addition of an emulsifier. FIG. 4 is a characteristic diagram showing the relationship between time until solidification starts and temperature when only an emulsifier is used and when an emulsifier and THF are added.
Claims (1)
レン系非イオン系界面活性剤を含む水とクロルフ
ルオルメタン系ゲスト分子とを接触させることを
特徴とする気体水化物の製造法。 ２ クロルフルオルメタン系ゲスト分子が、トリ
クロルフルオルメタン、ジクロルフルオルメタ
ン、モノクロルジフルオルメタンおよびジクロル
ジフルオルメタンよりなる群から選ばれた少なく
とも一つの有機物であることを特徴とする特許請
求の範囲第１項記載の気体水化物の製造法。 ３ 水に対して0.5〜５重量％のポリオキシエチ
レン系非イオン系界面活性剤と、水に対して0.5
〜８重量％のテトラハイドロフラン、フラン、メ
チルフランおよびメチルテトラハイドロフランよ
りなる群から選ばれた少なくも一つの化合物とを
含む水とクロルフルオルメタン系ゲスト分子とを
接触させることを特徴とする気体水化物の製造
法。[Claims] 1. A gaseous hydrate characterized by contacting water containing 0.5 to 5% by weight of a polyoxyethylene nonionic surfactant with chlorofluoromethane guest molecules. manufacturing method. 2. A patent characterized in that the chlorofluoromethane-based guest molecule is at least one organic substance selected from the group consisting of trichlorofluoromethane, dichlorofluoromethane, monochlorodifluoromethane, and dichlorodifluoromethane. A method for producing a gas hydrate according to claim 1. 3 0.5 to 5% by weight of polyoxyethylene nonionic surfactant based on water and 0.5% based on water
The chlorofluoromethane guest molecule is brought into contact with water containing ~8% by weight of at least one compound selected from the group consisting of tetrahydrofuran, furan, methylfuran and methyltetrahydrofuran. A method for producing gaseous hydrates.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12885178A JPS5555125A (en) | 1978-10-18 | 1978-10-18 | Preparation of gas hydrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12885178A JPS5555125A (en) | 1978-10-18 | 1978-10-18 | Preparation of gas hydrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5555125A JPS5555125A (en) | 1980-04-22 |
| JPS6159294B2 true JPS6159294B2 (en) | 1986-12-16 |
Family
ID=14994939
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12885178A Granted JPS5555125A (en) | 1978-10-18 | 1978-10-18 | Preparation of gas hydrate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5555125A (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6890444B1 (en) | 2003-04-01 | 2005-05-10 | Marine Desalination Systems, L.L.C. | Hydrate formation and growth for hydrate-based desalination by means of enriching water to be treated |
| US6497794B1 (en) | 1999-07-12 | 2002-12-24 | Marine Desalination Systems L.L.C. | Desalination using positively buoyant or negatively buoyant/assisted buoyancy hydrate |
| US6475460B1 (en) | 1999-07-12 | 2002-11-05 | Marine Desalination Systems Llc | Desalination and concomitant carbon dioxide capture yielding liquid carbon dioxide |
| US20040195160A1 (en) | 1999-07-12 | 2004-10-07 | Marine Desalination Systems, L.L.C. | Hydrate-based reduction of fluid inventories and concentration of aqueous and other water-containing products |
| US6565715B1 (en) | 1999-07-12 | 2003-05-20 | Marine Desalination Systems Llc | Land-based desalination using buoyant hydrate |
| US6673249B2 (en) | 2000-11-22 | 2004-01-06 | Marine Desalination Systems, L.L.C. | Efficiency water desalination/purification |
| US6969467B1 (en) | 1999-07-12 | 2005-11-29 | Marine Desalination Systems, L.L.C. | Hydrate-based desalination with hydrate-elevating density-driven circulation |
| US6767471B2 (en) | 1999-07-12 | 2004-07-27 | Marine Desalination Systems, L.L.C. | Hydrate desalination or water purification |
| JP2004501748A (en) | 2000-06-26 | 2004-01-22 | マリーン・ディサリネーション・システムズ・リミテッド・ライアビリティ・カンパニー | Desalination fractionator using artificial pressurized assist device where input water cooling is controlled by hydrate dissociation |
| US7008544B2 (en) | 2002-05-08 | 2006-03-07 | Marine Desalination Systems, L.L.C. | Hydrate-based desalination/purification using permeable support member |
| KR101009922B1 (en) | 2008-07-29 | 2011-01-20 | 에스티엑스조선해양 주식회사 | Method for the fast formation of gas hydrate |
| CN109455674B (en) * | 2018-12-21 | 2022-04-12 | 浙江埃森化学有限公司 | Solvent purification method of ethyl chloride byproduct sulfur |
-
1978
- 1978-10-18 JP JP12885178A patent/JPS5555125A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5555125A (en) | 1980-04-22 |
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