JPH0253474B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a sealant for a dry gas holder having a sealing cup. The structure of dry gas holders used to store blast furnace gas at steel plants and city gas at city gas plants is well known, but just to be sure, the main body is a large cylinder. The upper and lower sides of the side wall are surrounded by a roof and a bottom plate, within which a horizontal top cover moves up and down in contact with the side wall as gas flows in and out. The top lid contacts the side wall with an airtight sealing device provided with a sealing cup. The seal cup is filled with a sealant to prevent gas from escaping through the small gap with the side wall. This sealant gradually descends along the inner wall surface of the side wall, enters the bottom oil groove, and then, after removing water in the oil-water separator, is pushed up into the upper oil groove by an automatically controlled pump, and then returns to the side wall. It enters the seal cup along the inner wall surface to maintain gas tightness. Therefore, the sealant must be used in an amount that balances the gas pressure, and the liquid used must have an appropriate specific gravity and viscosity and be low in corrosive properties. It is required to have sufficient lubricity, and for this reason, all sealants conventionally used have been petroleum-based oily lubricants. For such a gas holder, the operation should be temporarily suspended while the gas is still stored, or normal operation should be stopped and the stored gas replaced with another gas, such as air, and the side walls of the gas holder etc. should be repaired using fire. It may be necessary to do so. At this time, repair work is carried out on huge gas holders using the top lid that moves up and down as a work platform for reasons of convenience and other reasons. Sparks caused by static electricity can cause the sealant in the seal cup to burn, and smoke can also be generated, which significantly impedes repair work and even poses a danger to workers from harmful gases and fire. Furthermore, in such a gas holder, it is unavoidable that the sealant used in the gas holder will seep out from the joints of the steel plates that make up the main body or minute gaps such as the rivets. It is also necessary to pay sufficient attention to contamination. In other words, petroleum-based lubricants conventionally used as sealants for gas holders are flammable and therefore extremely dangerous during repair work, and are not desirable from the standpoint of preventing unexpected accidents. . The present inventors have confirmed the above facts from their experience in the operation management of gas holders, have come to the recognition that the use of flammable petroleum-based oil lubricants as sealants should be avoided, and have developed an alternative sealant. As a result of extensive research and exploration, we have arrived at the present invention. An object of the present invention is to provide a sealant that is flame retardant, durable for long-term use, and free from the risk of pollution caused by water contamination, and which is significantly superior to conventional sealants. That is, the object 1) of the present invention is to provide a sealant capable of sufficiently and safely sealing the gas in the gas holder. Another object 2) of the present invention is to provide a sealant for the above-mentioned dry gas holder which can avoid the risk of pollution caused by water contamination. Still another object 3) of the present invention is to safely carry out repair work using fire on a seal cup filled with sealant during operation or suspension of a dry gas holder that stores blast furnace gas or city gas in a steelworks. To provide sealants. For the purpose of 1), appropriate specific gravity, viscosity and corrosion resistance are required. From the point of view of maintaining airtightness, it is preferable that the specific gravity is higher, but it is preferable to have a specific gravity of less than 1.0 because the current equipment that separates the mixed water into the lower layer and discharges it out of the system, which will be described later, can be used as is. preferable. In addition, if the viscosity is too low, it will become impossible to lubricate and pump the sliding parts of the top cover and side wall of the tank, and if it is too high, it will be difficult to pump and separate the mixed water.
The kinematic viscosity is preferably about 3 cst or more, particularly about 10 to 100 cst. The pour point must be such that it flows easily at atmospheric temperature, and in Japan it is usually -10
℃, preferably -30℃ or below considering the temperature in Hokkaido. For the purpose of 2), it must be able to be treated with general wastewater treatment. The sealant of the present invention is mainly composed of a glycol derivative containing a large amount of water in its composition in order to impart flame retardancy as described below. Water-glycol hydraulic oil is known as a composition that can contain water, but this type of glycol hydraulic oil has the disadvantage that it dissolves in water without restriction and is also freely soluble in water. Polyglycol, which is the main component of water, is famous as a compound that is difficult to treat in wastewater. On the other hand, although the sealant of the present invention may contain water within a certain range, it has the property of not absorbing any more water and discharging it out of the system, and is essentially soluble in water. Therefore, the content of organic matter in the aqueous layer is very low, and wastewater treatment is easy, and the risk of pollution caused by water pollution can be avoided. The organic layer can be disposed of by incineration, so there is no need for wastewater treatment. For the purpose of 3), the sealing agent of the present invention contains a considerable amount of water in its composition, has no flash point per se, and is a non-hazardous substance, thus achieving the purpose of 3). . The gas stored in the gas holder contains many components as shown in Table 1, and an important property required of the sealant is that the properties of the sealant do not change due to contact with these components. one of. Regarding this point, it was confirmed that the initial performance was not substantially impaired even when gas actually produced in a steelworks was fed into the sealant of the present invention over a long period of time. It has also been demonstrated that the sealant has excellent separation properties for dust mixed into the sealant.

[Table] Also, the amount of condensed water per commonly used gas holder is about 0.5 to 2 Kl/day. Therefore, among the impurities in the gas, water is the most common impurity that gets mixed into the sealant. Conventional mineral oil type seal oil does not dissolve water by itself, so a drainage point is provided at the bottom of the side wall of the gas holder to drain the mixed water out of the system. The water-glycol-based flame-retardant hydraulic oil, which has similar components to the sealant of the present invention, and the water-polyglycerin gas sealant described in JP-A No. 52-137713 can be used as a sealant by condensing from the gas. Since moisture is incorporated into the composition without limit, the viscosity, specific gravity, and amount of the sealant change, making it unsuitable as a sealant for permanent use. The sealant according to the present invention solves these problems. Therefore, the gist of the present invention is the general formula R ₁ —O(—R ₂ —O) _a (—C ₂ H ₄ O)— _b R ₃ (—O—C ₂ H
_Four
) _c (—O—R ₂ )— _d —O—R ₄ [wherein R ₁ and R ₄ are carbon atoms selected from the group consisting of an alkyl group and an alkyl-substituted aromatic group, with a carbon number of 8 to
24 monovalent hydrocarbon group, R ₂ O is oxypropylene group and/or oxybutylene group, R ₃ is methylene group or ethylene group, a, b, c, d are positive integers, and oxyethylene group and The weight ratio with the higher oxyalkylene group is 10/90 to 80/20, and the oxyethylene group and the higher oxyalkylene group mutually form a block copolymer, and the average molecular weight is in the range of 500 to 20,000. It is in. ]
polyoxyalkylene glycol diether represented by and the general formula R ₅ -O(-C ₂ H ₄ O) - _e H [wherein R ₅ is a hydrocarbon group having 5 to 8 carbon atoms, e is 1 or 2] represents a number. The present invention provides a flame-retardant sealant for a dry gas holder, characterized by comprising at least one compound selected from the group consisting of glycol monoethers represented by the following formula and water. The polyoxyalkylene glycol diether used in the present invention has the following general formula () R ₁ —O—(R ₂ —O)— _a (C ₂ H ₄ O)— _b R ₃ (—(O—
C ₂ H ₄ ) _c (—O—R ₂ )— _d —O—R ₄ (). In the above formula, R ₁ and R ₄ are the same or different linear or branched saturated monovalent aliphatic hydrocarbon groups (i.e. alkyl groups) or linear or branched alkyl-substituted monovalent aromatic hydrocarbon groups The number of carbon atoms is from 8 to 24, and examples include linear or branched octyl, nonyl, decyl, dodecyl, hexadecyl, octadecyl, hexyl phenyl, octylphenyl, xylyl. These are the basics. R ₂ O represents an oxypropylene group, an oxybutylene group or a mixed group thereof, and R ₃ represents a methylene group or an ethylene group. a, b, c, and d represent positive integers. The weight ratio of oxyethylene group to higher oxyalkylene group R ₂ O is about 10/90 to 80/20, particularly preferably 20/80 to 60/40. The oxyethylene group moiety and the higher oxyalkylene group moiety must mutually form a block copolymer, but when the oxyalkylene moiety R ₂ O is a mixed group of an oxypropylene group and an oxybutylene group, The propylene group portion and the oxybutylene group portion may be a random copolymer or a block copolymer. Further, the average molecular weight of the compound of formula () is about 500 to 20,000, and particularly preferably about 500 to 10,000. The compound of formula () can be produced, for example, using the method described in JP-A No. 48-22198 and JP-B No. 49-15185. That is, propylene oxide and/or butylene oxide is addition-polymerized to the alcohol or phenol of R ₁ OH, and then ethylene oxide is added-polymerized to obtain a polyoxyalkylene glycol monoether, and sodium alkoxide is added to this to give a polyoxyalkylene glycol monoether. It can be prepared by heating and mixing at ~150°C and gradually adding dihalogenated methylene or dihalogenated ethylene to the product to react.
Alternatively, polyoxyalkylene glycol monoether can be obtained by addition polymerizing propylene oxide and/or butylene oxide to R ₁ OH alcohol or phenol, then addition polymerizing ethylene oxide, and then adding polymerizing propylene oxide and/or butylene oxide. It can be prepared by a method in which the terminal OH group is etherified. The basic composition (A) of the flame-retardant sealant for dry gas holders according to the present invention consists of about 90-20% by weight of polyoxyalkylene glycol diether of the above formula () and about 10-80% by weight of water. Although this composition can retain a certain amount of water, it has the property that even if more water is mixed in, it will not dissolve and will be expelled from the system. Here, the hydrocarbon group R ₁ in the above formula (),
When the number of carbon atoms in R ₄ is less than 8, the water solubility becomes strong and the composition itself becomes easily soluble in water.
If the amount increases, the water retention properties of the composition will be lost. Compounds in which either or both of R ₁ and R ₄ are hydrogen have emulsifying properties and are therefore not suitable for the sealant of the present invention. The compound of the above formula () is a block copolymer in which higher oxyalkylene units are arranged at both ends of an oxyethylene unit,
It is a so-called reverse Pluronic type polyoxyalkylene glycol diether, and this structure provides the sealant of the present invention with its greatest characteristic of suppressing the saturated moisture content within a certain limit. Also here, oxyethylene group and oxyalkylene group R ₂ O
The reason why the ratio is limited is that if the ratio is smaller than 10/90, the saturated water content will be extremely low, and if it is larger than 80/20, the water solubility will be too high. Furthermore, when the molecular weight of the compound of formula () is less than about 500, it tends to evaporate easily, and the viscosity of the composition becomes low, and when the molecular weight is about 20,000 or more, the viscosity becomes too high, causing problems in circulation work, etc. Furthermore, if the amount of polyoxyalkylene glycol diether in formula () is too small, the property of keeping the saturated water content within a certain limit will be inhibited, the lubricity (viscosity) will decrease, and the amount of water will be too small. If it becomes too much, flame retardancy will be impaired. The second basic composition (B) of the flame-retardant sealant for gas holders according to the present invention has the following general formula () R ₅ - O (- C ₂ H ₄ O) - _e H () [In the formula, R ₅ is Straight chain or branched saturated or unsaturated aliphatic, alicyclic or aromatic hydrocarbon group having 5 to 8 carbon atoms, such as hexyl group, heptyl group, octyl group, benzyl group, tolyl group, xylyl group,
It represents a cyclohexyl group, etc., and e represents the number 1 or 2. It consists of a mixture of about 90 to 20% by weight of glycol monoether represented by ] and about 10 to 80% by weight of water. Although this composition can also retain a certain amount of water, it has the characteristic that even if more water is mixed in, it will not be absorbed and will be eliminated from the system as it is.
When the number of carbon atoms in the hydrocarbon group R ₅ in formula () is less than 5, it becomes water-soluble, and when the number of carbon atoms is more than 8, the composition loses its water retention properties. The polyoxyalkylene glycol diether of the above formula () has a relatively high specific gravity, and some have a higher specific gravity than water, so in that case, the specific gravity of the mixture with water will be higher than that of water. A mixture with a specific gravity higher than that of water can also be used as a sealant, but in order to use it as is in an existing dry gas holder that uses a mineral oil-based sealant, which has a specific gravity lower than that of water, a sealant with a specific gravity lower than that of water must be used. is good. Furthermore, the glycol monoether of the above formula () has a relatively low molecular weight, and its mixture with water has a relatively low viscosity, but the glycol monoether of the above formula () in which the _R5 group is an aliphatic hydrocarbon group has a specific gravity. is much lighter than water. Therefore, in order to reduce the specific gravity of the basic composition (A) or to increase the viscosity of the basic composition (B), the polyoxyalkylene glycol diether of the above formula () and the glycol monoether of the above formula () are combined. Basic composition (C) consisting of a mixture with water is practically preferred. In this basic composition (C), the blending ratio is about 90 to 20% by weight of the total amount of polyoxyalkylene glycol diether and glycol monoether, and about 20% by weight of water.
It preferably consists of about 45 to 10% by weight of polyoxyalkylene glycol diether, about 10 to 45% by weight of glycol monoether, and about 10 to 80% by weight of water. If the amount of polyoxyalkylene glycol diether and glycol monoether blended in this mixture is too small, the property of keeping the saturated water content within a certain limit will be inhibited, the viscosity will decrease, and the amount of water blended will be too small. This is the same as for basic compositions (A) and (B). The sealing agent according to the present invention can be sufficiently used if it consists only of the above basic composition (A), (B) or (C), but using these as a base oil, thickeners, diluents, additives, etc. are added as necessary. can do. An example suitable as a thickener or diluent is a polyoxyalkylene compound which is conventionally blended into conventional hydraulic fluids and brakes. Examples include polyoxypropylene glycol, monoethers or diethers thereof, poly(oxyethylene-oxypropylene) glycol copolymers, monoethers or diethers thereof, poly(oxyethylene-oxybutylene) glycol copolymers, monoethers or diethers thereof, These include addition polymerization of propylene oxide or a mixed alkylene oxide of propylene oxide and ethylene oxide to polyhydric alcohols such as oxypropylene triol, poly(oxyethylene-oxypropylene) triol, and sorbitol. These polyoxyalkylene compounds include monohydric alcohols such as methanol and ethanol, polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, and sorbitol, compounds with active hydrogen such as phenols, and amines, as well as propylene oxide and/or butylene oxide. Alternatively, it is produced by addition polymerizing a mixture of these alkylene oxides and ethylene oxide, and the terminal OH group is etherified as necessary. When blending these polyoxyalkylene compounds into the sealant according to the present invention, it is particularly advantageous to use water-insoluble compounds in terms of wastewater treatment. Suitably, the weight ratio of moiety and/or oxybutylene group moiety is about 50/50 or less. This copolymer may be a random copolymer or a block copolymer. In addition, when these polyoxyalkylene compounds are blended as thickeners or extenders, the molecular weight is about 500 or more, especially about 1,000 to 50,000.
Particularly preferred are those. Since the basic composition (B) described above has a low viscosity, it is particularly preferable to incorporate such a polyoxyalkylene compound. In order not to impair the water holding property within a certain limit and flame retardancy, which are the characteristics of the sealant of the present invention, the blending amount of these thickeners, extenders, and diluents should be determined according to the above-mentioned basic composition.
Up to about 50% by weight in the mixture of (A), (B) or (C) is suitable. The sealant of the present invention includes common lubricants, anticorrosives,
Additives such as antioxidants and antifoaming agents can be added as appropriate. Lubricant (oil improver,
The extreme pressure agent) may be anything as long as it dissolves in the composition of the present invention, examples of which include oils and fats, esters, mineral oil-based lubricating oils, synthetic lubricating oils, tricresyl phosphate, tricylenyl phosphate, etc. Phosphate esters of
These include aliphatic soaps such as potassium oleate, zinc dialkyl dithiophosphate, and the like. Any rust inhibitor or anticorrosive agent may be used as long as it dissolves in the composition of the present invention, and examples thereof include rosins such as abietic acid, ethanolamines, benzothiazoles, benzotriazoles, amines, amides, Carboxylic acid soaps such as lead naphthenate and aluminum stearate, sulfonic acid soaps such as calcium sulfonate, sulfonates, naphthenates, polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl phenol ethers, sorbitan fatty acid esters, Examples include nonionic surfactants such as polyoxyalkylene sorbitan fatty acid esters and polyoxyalkylene esters. Examples of antioxidants include bisphenols such as methylene-4,4-bis(2,6-di-tert-butylphenol), alkylphenols such as di-tert-butyl cresol, and naphthylamines. An example of an antifoaming agent is a silicone antifoaming agent. The amount of each of the above additives added to the sealant is approximately 0.1 to 2.0% by weight in the case of lubricants and rust/corrosion inhibitors.
In the case of antioxidants and antifoaming agents, each approximately
It is about 0.001 to 0.5% by weight. The remarkable effects of the sealant of the present invention include (1) it is superior to conventional mineral oil-based sealants in that it is not flammable because it contains a sufficient amount of water; and (2) it can be used for a long time. It is superior to known polyhydric alcohol compositions such as water-glycol type and water-polyglycerin type in that it can be used continuously without changing its properties (known polyhydric alcohol compositions do not change during use). (3) Since the properties change due to absorption of water, treatment such as distillation or evaporation is required for continued use.) and (3)
It should be noted that since it is essentially insoluble in water, there are no difficulties in wastewater treatment (by the way, known polyhydric alcohol compositions have low biodegradability and are difficult to treat if mixed into wastewater and spilled out). It should be. The following Examples will demonstrate that the composition of the present invention has excellent properties as a flame-retardant sealant for dry gas holders, but the present invention is not limited thereto. . In the examples, "parts" represent parts by weight unless otherwise specified. Example 1 Formula [RO(PO) _o (EO) _n ] - ₂ CH ₂ {R is 2-ethylhexyl group, PO is oxypropylene group, EO is oxyethylene group, m and n are integers, weight of EO/PO 29 parts of poly(oxyethylene-oxypropylene) glycol dioctyl ether, 28 parts of diethylene glycol monohexyl ether, 40 parts of water
1 part of rapeseed oil as a lubricant, 1.95 parts of morpholine as an anticorrosive agent, and 0.05 part of water-soluble silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Silicone KF-96) as an antifoaming agent. It has the properties shown in 2, and the gas ventilation test (gas flow rate per hour)
As shown in Table 3, no substantial change was observed even after 500 times sealant and gas flow period of 10 weeks). A similar test was conducted on water-glycol hydraulic oil, which is a general flame-retardant hydraulic oil, and the result was that the test oil was diluted by condensed water in the gas, resulting in a large amount of the test oil and overflowing from the test cylinder. The properties also changed significantly. Furthermore, a conventional petroleum-based sealant made of petroleum lubricating oil was tested in exactly the same manner. As shown in the table below, conventional petroleum sealants have a flash point and are combustible substances, but as they are used, they absorb and dissolve components in the gas, resulting in a considerable drop in viscosity and flash point, making them resistant to fire. becomes even more dangerous. In addition, for the ventilation test, sealant or test oil from No. 7 is placed in a cylindrical test cylinder (inner volume: approx. 15 mm) with a diameter of 150 mm and a height of 850 mm, and a test gas is fed into this test cylinder via a gas flow meter. I went.

【table】

[Table] Example 2 RO (PO) _o (EO) _n (PO) _o R {R is dodecyl group,
PO is an oxypropylene group, EO is an oxyethylene group, m and n are integers, 30 parts of poly(oxyethylene-oxypropylene) glycol decyl ether of a block copolymer with an EO/PO weight ratio of 20/80 and an average molecular weight of 1300, ethylene Table 4 shows the sealant of the present invention, which was composed of 30 parts of glycol monohexyl ether, 37 parts of water, 1 part of rapeseed oil as a lubricant, 1.95 parts of morpholine as an anticorrosive agent, and 0.05 part of water-soluble silicone oil as an antifoaming agent. As shown in Table 5, no substantial change was observed even after a gas ventilation test (600 times gas flow per hour/sealant, gas flow period 10 weeks). In the case of a general water-glycol hydraulic oil, which is a flame-retardant hydraulic oil that was similarly compared, the test oil was diluted by condensed water in the gas, and its properties changed significantly.

【table】

[Table] Example 3 Formula RO (PO) _o (EO) _n (PO) _o R {R is octylphenyl group, PO is oxypropylene group, EO is oxyethylene group, m and n are integers, EO/PO weight ratio of
10/90, block copolymer with an average molecular weight of 1400}
polyoxyalkylene glycol diether 60
Part, diethylene glycol monohexyl ether
The sealant of the present invention is composed of 10 parts of water, 27 parts of water, 1 part of lard oil as a lubricant, 1.95 parts of triethanolamine as an anticorrosive agent, and 0.05 parts of water-soluble silicone oil as an antifoaming agent. It showed no flash point and exhibited properties as a gas sealing agent, and did not show any particular change in properties even after a gas ventilation test (550 times the amount of gas ventilation per hour/sealant, gas flow period 10 weeks). Example 4 Formula [RO(PO) _o (EO) _n ] - ₂ CH ₂ {R is 2-ethylhexyl group, PO is oxypropylene group, EO is oxyethylene group, m and n are integers, weight of EO/PO 5 parts of polyoxyalkylene glycol diether (block copolymer with a ratio of 35/65 and an average molecular weight of 17,000), 80 parts of ethylene glycol monohexyl ether, 12 parts of water, 1 part of lard oil as a lubricant, 1.95 parts of morpholine as an anticorrosive agent, The sealant of the present invention, which is composed of 0.05 part of water-soluble silicone oil as a foaming agent, has a water content of 12wt%, exhibits no flash point, and exhibits properties as a gas sealant. 500x/sealing agent, gas flow period of 10 weeks), no particular change in properties was observed. Example 5 Formula [RO(PO) _o (EO) _n ] - ₂ CH ₂ {R is an octyl group, PO is an oxypropylene group, EO is an oxyethylene group, m and n are integers, and the weight ratio of EO/PO is 35 /
65, 20 parts of polyoxyalkylene glycol diether of block copolymer with an average molecular weight of 8500,
The sealant of the present invention, which is composed of 77 parts of water, 1 part of rapeseed oil as a lubricant, 1.95 parts of morpholine as an anticorrosive agent, and 0.05 parts of water-soluble silicone oil as an antifoaming agent, has a water content of 77 wt% and has no flash point. It exhibited properties as a gas sealant, and showed no particular change in properties even after a gas ventilation test (600 times the amount of gas ventilation per hour/sealant, gas flow period 10 weeks). Example 6 Formula [RO(PO) _o (EO) _n ] - ₂ CH ₂ {R is an octyl group, PO is an oxypropylene group, EO is an oxyethylene group, m and n are integers, the weight ratio of EO/PO is 75 /
25, 28 parts of polyoxyalkylene glycol dither of block copolymer with an average molecular weight of 1000,
Formula [RO(PO) _o (EO) _n ] - ₂ CH ₂ {R is octyl group,
PO is an oxypropylene group, EO is an oxyethylene group, m and n are integers, a weight ratio of EO/PO is 40/60, a block copolymer with an average molecular weight of 2500} 29 parts of polyoxyalkylene glycol diether, 40 parts of water
1 part rapeseed oil as a lubricant, 1.95 parts morpholine as an anticorrosive agent, and water-soluble silicone oil as an antifoaming agent.
The sealant of the present invention, which was composed of 0.05 parts, has a water content of 40wt%, exhibits no flash point, and exhibits properties as a gas sealant. Distribution period 10
No particular change in properties was observed even after 1 week). Example 7 Formula [RO(PO) _o (EO) _n ] - ₂ CH ₂ {R is an octyl group, PO is an oxypropylene group, EO is an oxyethylene group, m and n are integers, and the weight ratio of EO/PO is 75 /
25, 40 parts of polyoxyalkylene glycol diether of block copolymer with an average molecular weight of 5700,
The sealant of the present invention, which is composed of 57 parts of water, 1 part of rapeseed oil as a lubricant, 1.95 parts of morpholine as an anticorrosive agent, and 0.05 parts of water-soluble silicone oil as an antifoaming agent, has a water content of 57 wt% and no flash point. It exhibited properties as a gas sealing agent, and did not show any particular change in properties even after a gas ventilation test (500 times the amount of gas ventilation per hour/sealant, gas flow period 10 weeks). Example 8 Formula [RO(PO) _o (EO) _n ] - ₂ CH ₂ {R is a straight chain alkyl group with 24 carbon atoms (tetracosyl group; from 1-tetracosanol (manufactured by Tokyo Kasei) with a purity of about 97% ) PO is an oxypropylene group, EO is an oxyethylene group, m and n are integers, and the weight ratio of EO/PO
40/60, block copolymer with an average molecular weight of 2700}
Polyoxyalkylene glycol diether of 29
Part, diethylene glycol monohexyl ether
The sealant of the present invention is composed of 28 parts of water, 40 parts of water, 1 part of rapeseed oil as a lubricant, 1.95 parts of morpholine as an anticorrosive agent, and 0.05 parts of water-soluble silicone oil as an antifoaming agent. It exhibited properties as a gas sealing agent without showing any specks, and did not show any particular change in properties even after a gas ventilation test (500 times the amount of gas ventilation per hour/sealant, gas flow period 10 weeks). Example 9 Formula [BO (BO) _o (EO) _n ] - ₂ CH ₂ {R is an octyl group, BO is an oxybutylene group, EO is an oxyethylene group, m and n are integers, the weight ratio of EO/BO is 35 /65,
Polyoxyalkylene glycol dialkyl ether of block copolymer with an average molecular weight of 2300 29
Part, diethylene glycol monohexyl ether
The sealant of the present invention, which is composed of 28 parts, 40 parts water, 1 part lard oil as a lubricant, 1.95 parts morpholine as an anticorrosive agent, and 0.05 parts water-soluble silicone oil as an antifoaming agent, has a water content of 40 wt% and a flash point. It exhibited properties as a gas sealing agent, and did not show any particular change in properties even after a gas ventilation test (500 times the amount of gas ventilation per hour/sealant, gas flow period 10 weeks). Examples 10 and 11 It was confirmed that the compositions shown in the following table had properties as gas sealants, and that their initial performance hardly changed even after testing in a gas flow machine.

[Table] Properties after gas flow test (gas flow period 10 weeks, gas flow rate per hour/sealant =
500/1) is shown in Table 7.

[Table] Example 12 It was confirmed that the composition shown in the following table had properties as a gas sealing agent, and that the initial performance hardly changed even after the gas flow test.

[Table] Properties after gas flow test (gas flow period 10 weeks, gas flow rate per hour/sealant =
500/1) is shown in Table 9.

【table】

Claims (1)

[Claims] 1 General formula R ₁ —O—(R ₂ —O)— _a —(C ₂ H ₄ O)— _b R ₃ —(O
—C ₂ H ₄ )— _c —(O—R ₂ )— _d —O—R ₄ [wherein R ₁ and R ₄ are carbon atoms selected from the group consisting of an alkyl group and an alkyl-substituted aromatic group]
24 monovalent hydrocarbon group, R ₂ O is oxypropylene group and/or oxybutylene group, R ₃ is methylene group or ethylene group, a, b, c, d are positive integers, and oxyethylene group and The weight ratio with the higher oxyalkylene group is 10/90 to 80/20, and the oxyethylene group and the higher oxyalkylene group mutually form a block copolymer, and the average molecular weight is in the range of 500 to 20,000. It is in. ]
polyoxyalkylene glycol diether represented by and the general formula R ₅ -O(-C ₂ H ₄ O) - _e H [wherein R ₅ is a hydrocarbon group having 5 to 8 carbon atoms, e is 1 or 2] represents a number. A flame-retardant sealant for a dry gas holder, characterized by comprising at least one compound selected from the group consisting of glycol monoethers represented by the following formula and water. 2 General formula R ₁ -O (-R ₂ -O) _a (-C ₂ H ₄ O) - _b R ₃ (-O-C ₂ H
_Four
) _c (—O—R ₂ )— _d —O—R ₄ [wherein R ₁ and R ₄ are carbon atoms selected from the group consisting of an alkyl group and an alkyl-substituted aromatic group, with a carbon number of 8 to
24 monovalent hydrocarbon group, R ₂ O is oxypropylene group and/or oxybutylene group, R ₃ is methylene group or ethylene group, a, b, c, d are positive integers, and oxyethylene group and The weight ratio with the higher oxyalkylene group is 10/90 to 80/20, and the oxyethylene group and the higher oxyalkylene group mutually form a block copolymer, and the average molecular weight is in the range of 500 to 20,000. It is in. ]
The sealing agent according to claim 1, characterized in that it consists of a polyoxyalkylene glycol diether represented by: and water. 3 General Formula R ₅ —O(—C ₂ H ₄ O)— _e H [In the formula, R ₅ represents a hydrocarbon group having 5 to 8 carbon atoms, and e represents the number of 1 or 2. ] The sealing agent according to claim 1, characterized in that it is composed of a glycol monoether represented by the following formula and water. 4 General formula R ₁ -O (-R ₂ -O) _a (-C ₂ H ₄ O) - _b R ₃ -(O-
C ₂ H ₄ ) _c (—O—R ₂ )— _d —O—R ₄ [In the formula, R ₁ and R ₄ have 8 to 8 carbon atoms selected from the group consisting of an alkyl group and an alkyl-substituted aromatic group.
24 monovalent hydrocarbon group, R ₂ O is oxypropylene group and/or oxybutylene group, R ₃ is methylene group or ethylene group, a, b, c, d are positive integers, and oxyethylene group and The weight ratio with the higher oxyalkylene group is 10/90 to 80/20, and the oxyethylene group and the higher oxyalkylene group mutually form a block copolymer, and the average molecular weight is in the range of 500 to 20,000. It is in. ]
polyoxyalkylene glycol diether represented by and the general formula R ₅ -O(-C ₂ H ₄ O) - _e H [wherein R ₅ is a hydrocarbon group having 5 to 8 carbon atoms, e is 1 or 2] represents a number. ] The sealing agent according to claim 1, characterized by comprising a glycol monoether represented by the following formula and water.