CN102712474A - Mixtures of alkali polysulfides - Google Patents
Mixtures of alkali polysulfides Download PDFInfo
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- CN102712474A CN102712474A CN2010800606647A CN201080060664A CN102712474A CN 102712474 A CN102712474 A CN 102712474A CN 2010800606647 A CN2010800606647 A CN 2010800606647A CN 201080060664 A CN201080060664 A CN 201080060664A CN 102712474 A CN102712474 A CN 102712474A
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- alkali
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/10—Liquid materials
- C09K5/12—Molten materials, i.e. materials solid at room temperature, e.g. metals or salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/22—Alkali metal sulfides or polysulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/22—Alkali metal sulfides or polysulfides
- C01B17/34—Polysulfides of sodium or potassium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
Abstract
The present invention relates to mixtures of alkali polysulfides and mixtures of alkali polysulfides and alkali thiocyanates, to a method for the production of same, to the use thereof as heat transfer media or heat storage media, and to heat transfer media or heat storage media comprising the mixtures of alkali polysulfides or the mixtures of alkali polysulfides and alkali thiocyanates.
Description
The present invention relates to the mixture of alkali metals polysulfide; The mixture of alkali metals polysulfide and alkali metal thiocyanate; Its preparation method, it is as conducting heat or the purposes of thermal storage fluid and heat transfer or the thermal storage fluid that comprises the mixture of alkali metals polysulfide or comprise the mixture of alkali metals polysulfide and alkali metal thiocyanate.
The fluid that is used for transporting heat energy is used for various industrial circles.In oil engine, the mixture of water and terepthaloyl moietie transfers to scatterer with the combustion heat.Similar compound transfers to heat in the regenerative apparatus by sun power roof heat collector.In chemical industry, its with heat by the system transmissions of electricity or fossil oil heating to reaction apparatus, perhaps transfer in the refrigerating unit by the latter.
Based on application,, therefore use multiple fluid in practice to conducting heat or there is very big-difference in the composite request of thermal storage fluid.Said fluid should be liquid and perhaps even under the lower temperature has LV in room temperature.As far as higher application of temperature, water no longer is an option; Its vp becomes too high.Therefore; Alkyl MO is used under the temperature of about at the most 320 ° of C; Synthetic is contained under the temperature that aromatic oil or silicone oil is used for 400 ° of C at the most (VDI
VDI-Gesellschaft Verfahrenstechnik und Chemieingenieurwesen, Springer Verlag Berlin Heidelberg 2006).
The new challenge that heat-transfer fluid ran into is the solar heat power station (Butscher, R., Bild der Wissenschaft 2009,3,84-92 page or leaf) that produces electric energy on a large scale.Up to now, the installed power that amounts to hundreds of approximately megawatts has been built in this type power station, and many other power stations are also among planning, especially in Spain, and in the north African and the U.S..Solar radiation for example focuses on the focal line of said minute surface by parabolic minute surface groove.Existence is positioned at Glass tubing inside to prevent the metal tube of thermosteresis at the focal line place, wherein the space between the said concentric tube is vacuumized.The heat-transfer fluid said metal tube of flowing through.At present, use the mixture of phenyl ether and biphenyl in this case.Said heat transfer reagent is heated to the temperature of 400 ° of C at the most, is used to make the vapour generator operation of wherein water generation evaporation.This steam driven turbine, this is the such generator that drives of conventional power plant and for example.Therefore, obtain about 30% peak efficiencies, based on the intrinsic energy of incident sunlight.The efficient of turbine under this temperature in is about 37%.
Depress under about 256 ° of C at standard atmosphere as two kinds of compositions of the mixture of the phenyl ether of heat transfer reagent and biphenyl and to seethe with excitement.The fusing point of biphenyl is 68-72 ° of C, and the fusing point of phenyl ether is 26-39 ° of C.The mixing of these two kinds of materials is reduced to 12 ° of C with fusing point.The mixture of said two kinds of materials can be used for being at most the temperature of 400 ° of C; Under higher temperature, can decompose.Vp under this temperature is about 10 crust, and this pressure is still industry and goes up tolerable.
In order to obtain to be higher than 37% turbine efficiency, must adopt higher steam-in temperature.Efficiency of Steam Turbine improves along with the raising of turbine temperature in.The modern electro of combustion of fossil fuels stands under the steam-in temperature of 650 ° of C at the most and works, and obtains about 45% efficient thus.Might the heat-transfer fluid in the minute surface focal line be heated to about 650 ° of C fully in the industry, the so high efficient of same thus acquisition; Yet this receives the limited stable on heating obstruction of used heat-transfer fluid up till now.
In the solar column power station, can obtain than the higher temperature in para-curve groove power station, in said solar column power station, a tower is focused on sunlight the mirror encirclement of the susceptor on this tower top.In this susceptor, heat transfer reagent is heated, use it for by interchanger and produce steam and make steam turbine operation.In the tower power station (Solar II, California) in, with SODIUMNITRATE (NaNO
3) and saltpetre (KNO
3) (60:40) mixture is as heat transfer reagent.This mixture can use under up to 550 ° of C and not produce any problem, but has the high fusing point of 240 ° of C.
The organic substance that up to now can withstand long term exposure be higher than 400 ° of C temperature is still unknown.Some dimethyl siloxanes or diphenyl siloxane base oil can perhaps even under the high slightly temperature use in the temperature up to 400 ° of C equally.Right heat, its high cost has hindered its application in the solar heat power station.
Another kind of selection is to use known Liquid Sodium or sodium-potassium-sodium alloy heat transfer reagent in the nuclear technique.Yet the preparation of these metals is extremely expensive, and it reacts with trace water, thereby discharges hydrogen, and this causes security challenge.
In addition, known lower melting point solder flux metal, for example Wood's metal (Bi-Pb-Cd-Sn alloy, fusing point are about 75 ° of C).Yet high proportion has hindered its application as heat-transfer fluid.
Proposed other the possible high temperature heat transfer reagent based on sulphur, it is for example to use (WO2005/071037) with the form of mixtures of small amounts of selenium and/or tellurium.Liquid sulfur is problematic as heat transfer reagent, because it has HV and can't be with this form pumping under 150-200 ° of C.Viscosity can reduce (US4335578) through additive such as bromine or iodine, but it has highly corrosive.
Technically also can use the water that is under the corresponding high pressure.Yet this receives in the obstruction that is higher than the high vp that is higher than 270 crust under 500 ° of C temperature, and this makes the many km pipelines in the solar heat power station become expensive wastefully.Steam self is disadvantageous as heat transfer reagent, because it has lower thermal conductivity and low heat capacity with the liquid phase ratio.
Another selection is to use the inorganic salt melt as heat-transfer fluid.This type salt-melting is the prior art of the method for at high temperature working.The eutectic mixture of saltpetre, SODIUMNITRATE and Sodium Nitrite has fusing point and the commercially available acquisition of 146 ° of C.Yet, being limited to 450 ° of C on the use temperature, this is because nitrite significantly resolves into nitrous gases, alkalimetal oxide and elemental nitrogen under this temperature being higher than.The eutectic mixture of SODIUMNITRATE and saltpetre can use under the temperature of 600 ° of C at the most.Yet this mixture is problematic as the heat-transfer fluid in the solar heat power station, because it has the HMP of about 220 ° of C.When temperature is brought down below fusing point,, can cause the salt in the pipeline to solidify for example at night or during low solar radiation.This must prevent that because can produce local stress during the fusion again, this can damage device.Can carry out anti-frost protection to accompany hot form, but this extremely difficult technically enforcement, and very expensive as far as this high temperature in addition.The fusing point of the mixture of SODIUMNITRATE and saltpetre can reduce (Bradshaw, R.W. through adding lithium nitrate or nitrocalcite; Meeker, D.E.; Solar Energy Materials 1990, the 21 volumes, the 51-60 page or leaf).Yet because expensive and uneconomical, and the existence of calcium promotes that nitrate salt resolves into nitrite and oxygen with the mixture of lithium nitrate, so the use temperature upper limit reduces along with the rising of calcium contents.
In addition, also can use metal halide as heat-transfer fluid.The problem that produce this moment is that halogenation fluid (especially at elevated temperatures) causes Corrosion of Metallic Materials problem to be used usually.
Should have lower melting point on the theory of mixtures of the mixture of alkali metals polysulfide, especially sodium polysulphide and potassium polysulfide and can be used for up to 500 ° of C or even higher temperature under.According to calculating, the phasor of ternary sodium sulphite-potassium sulphide-sulfur system should have constant low melting glass point: K to following composition
0.84Na
0.26S
3.61(78 ° of C), K
0.77Na
0.23S
3.75(73 ° of C) and K
0.79Na
0.21S
3.95(83 ° of C) (Lindberg, D.; Backman, R.; Hupa, M.; Chartrand, P.; J.Chem.Therm.2006, the 38th volume, 900-915 page or leaf).The testing data of this ternary system not.In sodium sulphite-sulfur system, fusing point can be reduced to about 120 ° of C (Sangster, J.; Pelton, A.D.; J.Phase Equil.1997, the 18th volume, the 82nd page).A shortcoming of alkali metals polysulfide is that it has viscosity higher under molten state, especially sodium polysulphide (Cleaver, B.; Davis, A.J.; Electrochimica Acta 1973, the 18 volumes, the 727-731 page or leaf).
DE3824517 has described the mixture of alkali metal thiocyanate, and especially the mixture of Rhocya and Sodium Thiocyanate 99 is as the purposes of heat-transfer fluid.Rhocya fusion under 173 ° of C, Sodium Thiocyanate 99 fusion under 310 ° of C.Have 73 moles of % Rhocyas and the eutectic mixture of said two kinds of salt of the ratio of 27 moles of % Sodium Thiocyanate 99s and have the fusing point of about 130 ° of C.But said melt has LV and therefore pumping, and does not improve energy cost.
A shortcoming of alkali metal thiocyanate is that it has just begun to decompose under the temperature that is higher than 450 ° of C.Except sulphur, also form more dystectic alkali metal cyanide (Gmelins Handbuch der Anorganischen Chemie 1938, the 22 volumes, the 899th page).
The fusing point of alkali metal thiocyanate can further reduce through adding other salt.Especially add nitrite or nitrate and can reduce fusing point.Yet, adding the oxidisability nitrite or nitrate and cause explosive the decomposition at elevated temperatures, this can extraly quicken through any dissolved trace heavy metal.Therefore, discharged the application of this type mixture in industrial applications.
Another problem comes from the following fact: purpose is to move the solar heat power station continuously.This can be through at high solar radiation storage heat, during the weather of sunset or difference, uses it for generating and realizes.Heat can be through directly being stored in the heat-transfer medium of heating in the storage tank of well insulated, perhaps indirectly heat is passed to another storage medium and stores.
Indirect method is used in Hispanic 50MW Andasol I power station, wherein uses the melt (60:40 of 28000 tons of SODIUMNITRATE and saltpetre; Weight %).During solar radiation, said melt is pumped in the hot groove via oil-salt interchanger by colder groove (about 280 ° of C), be heated to about 380 ° of C during this period.When low solar radiation and night, the power station can be with about 7.5 hours of the storage medium oepration at full load that is full of (www.solarmillennium.de/upload/Download/Technologie/Andas ol1-3deutsch.pdf).Yet, use heat-transfer fluid as thermal storage fluid also advantageously, because can therefore save corresponding oil-salt interchanger.Since the high-vapor-pressure of said oil and compare with nitrate salt expensive, do not consider this point up to now as yet.
The purpose of this invention is to provide a kind of improved heat transfer and thermal storage fluid that is easy to get.Said fluid should preferably use under the temperature that is higher than 500 ° of C in the temperature that is higher than 400 ° of C.Simultaneously, fusing point should preferably be lower than 200 ° of C at least.In addition, the said liquid controllability that should possess skills, minimum vp preferably is lower than 10 crust.
Said purpose is passed through the mixture of alkali metals polysulfide and is realized according to the present invention.
Therefore, the present invention provides the mixture of the alkali metals polysulfide of following general formula:
(M
1 xM
2 (1–x))
2S
y
M wherein
1, M
2=Li, Na, K, Rb, Cs, and M
1Be different from M
2, 0.05≤x≤0.95 and 2.0≤y≤6.0.
In a preferred embodiment of the invention, M
1=K and M
2=Na.
In another preferred embodiment of the present invention, 0.20≤x≤0.95.In special preferred embodiment of the present invention, 0.50≤x≤0.90.
In another preferred embodiment of the present invention, 3.0≤y≤6.0.In special preferred embodiment of the present invention, y=4.0,5.0 or 6.0.
In special preferred embodiment of the present invention, M
1=K, M
2=Na, 0.20≤x≤0.95 and 3.0≤y≤6.0.
In very particularly preferred embodiment of the present invention, M
1=K, M
2=Na, 0.50≤x≤0.90 and y=4.0,5.0 or 6.0.
Another embodiment relates to and consists of (K
(1-x)Na
x)
2S
zAlkali metals polysulfide, wherein x=0-1 and z=2.3-3.5, preferred x=0.5-0.7 and z=2.4-2.9.
Another embodiment relates to alkali metals polysulfide (Na
0.5-0.65K
0.5-0.35)
2S
2.4-2.8Perhaps has composition (Na
0.6K
0.4)
2S
2.6Those.
Mixture of the present invention is characterised in that low especially fusing point.In a preferred embodiment of the invention, the fusing point of mixture of the present invention is lower than 200 ° of C, is lower than 160 ° of C in particularly preferred embodiments.
Mixture of the present invention has high thermal stability.In a preferred embodiment of the invention, mixture of the present invention is under the temperature up to 450 ° of C, and is in particularly preferred embodiments under the temperature up to 500 ° of C, stable in unusual particularly preferred embodiment even under up to the temperature of about 500 ° of C.
In a preferred embodiment of the invention, mixture of the present invention under 500 ° of C, have be lower than 5 the crust, more preferably less than 2 the crust vp.
The preparation of alkali metals polysulfide is known and can be for example through alkali metalsulphide and reaction of Salmon-Saxl is carried out.A kind of alternative method is to make the direct and reaction of Salmon-Saxl of basic metal, and is said to sodium like US4640832.The basic metal that is in the liquefied ammonia and the reaction of sulphur have been described equally.Another synthetic selection is that alkali metal hydrosulfide or alkali metalsulphide and sulphur are reacted in alcoholic solution.
The present invention further provides a kind of method for preparing alkali metals polysulfide mixture of the present invention, and it is included in protective gas or under reduced pressure heats corresponding alkali metalsulphide and sulphur, is perhaps adding or do not adding the corresponding alkali metals polysulfide of heating under the sulphur.
In the preferred embodiment of the inventive method, starting substance is heated at least 400 ° of C reaches at least 0.5 hour.
Suitable protective gas is a rare gas, preferred argon gas or nitrogen.
The present invention further provides a kind of method for preparing alkali metals polysulfide mixture of the present invention, and it comprises reacts corresponding alkali-metal liquid ammonia solution and sulphur under protective gas.
The present invention further provides the purposes of alkali metals polysulfide mixture of the present invention as heat transfer or thermal storage fluid.
In a preferred embodiment of the invention; Alkali metals polysulfide mixture of the present invention is not containing use under air or the moisture; Preferably in the closed system of for example pipeline, pump, control unit and container, use, to prevent said heat transfer or thermal storage fluid hydrolytic reactions or oxidizing reaction in operational process.
The present invention further provides heat transfer or the thermal storage fluid that comprises alkali metals polysulfide mixture of the present invention.
When alkali metals polysulfide mixture of the present invention mixed with alkali metal thiocyanate, its Application Areas can further be widened.
The present invention further provides the alkali metals polysulfide of following general formula and the mixture of alkali metal thiocyanate:
((M
1 xM
2 (1–x))
2S
y)
m(M
3 zM
4 (1–z)SCN)
(1–m)
M wherein
1, M
2, M
3, M
4=Li, Na, K, Rb, Cs and M
1Be different from M
2, M
3Be different from M
4, and 0.05≤x≤1,0.05≤z≤1,2.0≤y≤6.0 and m be mol ratio, wherein 0.05≤m≤0.95.
In a preferred embodiment of the invention, M
1And M
3=K and M
2And M
4=Na.
In a preferred embodiment of the invention, 0.20≤x≤1.In special preferred embodiment of the present invention, 0.50≤x≤1.
In another preferred embodiment of the present invention, 3.0≤y≤6.0.In special preferred embodiment of the present invention, y=4.0,5.0 or 6.0.
In another preferred embodiment of the present invention, 0.20≤z≤1.In special preferred embodiment of the present invention, 0.50≤z≤1.
In another preferred embodiment of the present invention, 0.20≤m≤0.80.In special preferred embodiment of the present invention, 0.33≤m≤0.80.
In special preferred embodiment of the present invention, M
1And M
3=K, M
2And M
4=Na, 0.20≤x≤1,0.20≤z≤0.95,3.0≤y≤6.0 and 0.20≤m≤0.95.
In very particularly preferred embodiment of the present invention, M
1And M
3=K, M
2And M
4=Na, 0.50≤x≤1,0.50≤z≤0.95, y=4.0,5.0 or 6.0 and 0.33≤m≤0.80.
In another particularly preferred embodiment of the present invention, M
1And M
3=K, x=1, z=1, y=4.0,5.0 or 6.0 and 0.33≤m≤0.80.
In another particularly preferred embodiment of the present invention, M
1And M
3=K, x=1, z=1, y=4 and m=0.5.
In another particularly preferred embodiment of the present invention, M
1And M
3=K, x=1, z=1, y=5 and m=0.5.
In another particularly preferred embodiment of the present invention, M
1And M
3=K, x=1, z=1, y=6 and m=0.5.
Find that surprisingly alkali metals polysulfide of the present invention is more thermally-stabilised than independent alkali metal thiocyanate with the mixture of alkali metal thiocyanate.In addition, the viscosity of the mixture of alkali metals polysulfide of the present invention and alkali metal thiocyanate is lower than the viscosity of the alkali metals polysulfide mixture of alkali-free metal thiocyanate salt.
The preparation of alkali metal thiocyanate is known and implements with technical scale.
The present invention further provides a kind of method for preparing the mixture of alkali metals polysulfide of the present invention and alkali metal thiocyanate, comprises alkali metals polysulfide and alkali metal thiocyanate congruent melting are melted.Said method also can be carried out when stirring melt.
The mixture of alkali metals polysulfide of the present invention and alkali metal thiocyanate is applicable to the high temperature application scenario of the heat transfer reagent that needs wide fluid temperature scope usually.
The present invention further provides the purposes of the mixture of alkali metals polysulfide of the present invention and alkali metal thiocyanate as heat transfer or thermal storage fluid.
In a preferred embodiment of the invention; The mixture of alkali metals polysulfide of the present invention and alkali metal thiocyanate is not containing use under air and the moisture; Preferably in the closed system of for example pipeline, pump, control unit and container, use, to avoid said heat transfer or thermal storage fluid hydrolytic reactions or oxidizing reaction in operational process.
The present invention further provides conducts heat or thermal storage fluid, and it comprises the mixture of alkali metals polysulfide of the present invention and alkali metal thiocyanate.
Embodiment
1. synthetic sodium-potassium polysulfide (K
xNa
1 – x)
2S
y
A) through making the mixture fusion of alkali metals polysulfide and sulphur
K
2S
3And Na
2S
4Starting substance prepares according to literature method.
Synthetic Na
0.464K
1.536S
3.745
With 3.51g K
2S
3, 0.43g sulphur and 1.06g Na
2S
4Be heated to 400 ° of C in the silica glass ampoule in airtight vacuumizing and reach 30 minutes, then this melt is cooled to room temperature.In the argon gas glove box, open this ampoule, and redness to pale red-yellow solid is smash through pestle and pulverized (quantitative yield).The fusion in 151-157 ° of C scope of said solid.
Synthetic Na
0.42K
1.58S
3.80
With 3.65g K
2S
3, 0.49g sulphur and 0.95g Na
2S
4Be heated to 400 ° of C in the silica glass ampoule in airtight vacuumizing and reach 30 minutes, then this melt is cooled to room temperature.In the argon gas glove box, open this ampoule, and redness to pale red-yellow solid is smash through pestle and pulverized (quantitative yield).The fusion in 158-167 ° of C scope of said solid.
Synthetic Na
0.325K
1.675S
3.61
With 3.87g K
2S
3, 0.38g sulphur and 0.75g Na
2S
4Be heated to 400 ° of C in the silica glass ampoule in airtight vacuumizing and reach 30 minutes, then this melt is cooled to room temperature.In the argon gas glove box, open this ampoule, and redness to pale red-yellow solid is smash through pestle and pulverized (quantitative yield).The fusion in 157-163 ° of C scope of said solid.
B) through basic metal and sulphur are reacted in liquefied ammonia
Synthetic Na
0.46K
1.54S
3.75
This synthesizes under argon gas atmosphere and is undertaken by Schlenk and glove box technology.At first 63.6g (1.98 moles) sulphur is added and be in the glass flask in-30 ° of C liquefied ammonia.Subsequently, under agitation drip 5.50g (0.24 mole) sodium Metal 99.5 be in about 800ml liquefied ammonia (30 ° of C) and the blue solution of 32.0g (0.81 mole) potassium metal.The gained mixture heating up to room temperature, and is stirred and to evaporate until ammonia.Make the gained orange solids under decompression (about 1 millibar), remove ammonia under 150 ° of C subsequently.The fusion in 166-169 ° of C scope of said solid.
Synthetic Na
0.23K
1.77S
3.75
This synthesizes under argon gas atmosphere and is undertaken by Schlenk and glove box technology.At first 43.0g (1.34 moles) sulphur is added and be in the glass flask in-30 ° of C liquefied ammonia.Subsequently, under agitation drip 1.82g (0.079 mole) sodium Metal 99.5 be in about 800ml liquefied ammonia (30 ° of C) and the blue solution of 24.9g (0.63 mole) potassium metal.The gained mixture heating up to room temperature, and is stirred and to evaporate until ammonia.Make the gained orange solids under decompression (about 1 millibar), remove ammonia under 150 ° of C subsequently.The fusion in 165-166 ° of C scope of said solid.
2. (K
xNa
1-x)
2S
ySynthetic and character with the mixture of alkali metal thiocyanate
A) synthetic
Method 1:
Potassium polysulfide (K with respective amount
2S
x) or potassium polysulfide sodium ((K
xNa
1-x)
2S
y) be heated to 400 ° of C in the silica glass ampoule in airtight vacuumizing and reach 30 minutes with Rhocya (KSCN), then this melt is cooled to room temperature.In the argon gas glove box, open this ampoule, and molten product smash through pestle pulverize.This obtains orange solids, and its melting range is as shown in table 1.
Method 2:
Potassium polysulfide (K with respective amount
2S
x) or potassium polysulfide sodium ((K
xNa
1 – x)
2S
y) under argon gas atmosphere, mix in glass flask with Rhocya (KSCN) and be heated to 180 ° of C.Stir said mixture until forming homogeneous melt, be cooled to room temperature then.This obtains orange solids, its melting range and the solid melting range identical (referring to table 1) for preparing according to method 1.
Table 1
| Form | Melting range [° C] |
| (K 2S 4) 0.67(KSCN) 0.33 | 123-125 |
| (K 2S 4) 0.50(KSCN) 0.50 | 110-112 |
| (K 2S 4) 0.33(KSCN) 0.67 | 128-130 |
| (K 2S 5) 0.50(KSCN) 0.50 | 150-158 |
| (K 2S 6) 0.50(KSCN) 0.50 | 146-153 |
| (Na 0.46K 1.54S 3.75) 0.50(KSCN) 0.50 | 92-100 |
| (Na 0.46K 1.54S 3.75) 0.45(KSCN) 0.55 | 94-110 |
| (Na 0.23K 1.77S 3.75) 0.67(KSCN) 0.33 | 100-108 |
| (Na 0.23K 1.77S 3.75) 0.53(KSCN) 0.47 | 98-102 |
| (Na 0.23K 1.77S 3.75) 0.50(KSCN) 0.50 | 82-96 |
| (Na 0.23K 1.77S 3.75) 0.48(KSCN) 0.52 | 80-90 |
| (Na 0.23K 1.77S 3.75) 0.33(KSCN) 0.67 | 80-96 |
B) viscosity
Melt viscosity is passed through rotary viscosity design determining.
Table 2
C) thermostability
Mixture (K is used in the test of thermostability
2S
4)
0.5(KSCN)
0.5(melting range 110-112 ° C), (K
2S
5)
0.5(KSCN)
0.5(melting range 150-158 ° C) and (K
2S
6)
0.5(KSCN)
0.5(melting range 146-153 ° C) carries out.
Stability under 400 °:
3g is consisted of (K
2S
4)
0.5(KSCN)
0.5Mixture under 400 ° of C, in the glass ampoule that vacuumizes, store 28 days.The melting range of this mixture does not change.
3g is consisted of (K
2S
5)
0.5(KSCN)
0.5Mixture under 400 ° of C, in the glass ampoule that vacuumizes, store 28 days.The melting range of this mixture does not change.
3g is consisted of (K
2S
6)
0.5(KSCN)
0.5Mixture under 400 ° of C, in the glass ampoule that vacuumizes, store 28 days.The melting range of this mixture does not change.
Stability under 450 ° of C:
3g is consisted of (K
2S
4)
0.5(KSCN)
0.5Mixture under 450 ° of C, in the glass ampoule that vacuumizes, store 28 days.The melting range of this mixture does not change.
3g is consisted of (K
2S
5)
0.5(KSCN)
0.5Mixture under 450 ° of C, in the glass ampoule that vacuumizes, store 28 days.The melting range of this mixture does not change.
3g is consisted of (K
2S
6)
0.5(KSCN)
0.5Mixture under 450 ° of C, in the glass ampoule that vacuumizes, store 28 days.The melting range of this mixture does not change.
Stability under 500 ° of C:
3g is consisted of (K
2S
4)
0.5(KSCN)
0.5Mixture under 500 ° of C, in the glass ampoule that vacuumizes, store 28 days.The melting range of this mixture does not change.
3g is consisted of (K
2S
5)
0.5(KSCN)
0.5Mixture under 500 ° of C, in the glass ampoule that vacuumizes, store 28 days.The melting range of this mixture does not change.
3g is consisted of (K
2S
6)
0.5(KSCN)
0.5Mixture under 500 ° of C, in the glass ampoule that vacuumizes, store 28 days.The melting range of this mixture does not change.
Stability under 600 ° of C:
3g is consisted of (K
2S
4)
0.5(KSCN)
0.5Mixture under 600 ° of C, in the glass ampoule that vacuumizes, store 28 days.The melting range of this mixture does not change.
3g is consisted of (K
2S
5)
0.5(KSCN)
0.5Mixture under 600 ° of C, in the glass ampoule that vacuumizes, store 28 days.The melting range of this mixture does not change.
3g is consisted of (K
2S
6)
0.5(KSCN)
0.5Mixture under 600 ° of C, in the glass ampoule that vacuumizes, store 28 days.The melting range of this mixture does not change.
Claims (24)
1. the alkali metals polysulfide mixture of a following general formula:
(M
1 xM
2 (1–x))
2S
y
M wherein
1, M
2=Li, Na, K, Rb, Cs, and M
1Be different from M
2, 0.05≤x≤0.95 and 2.0≤y≤6.0.
2. according to the mixture of claim 1, M wherein
1=K and M
2=Na.
3. according to the mixture of claim 1 or 2,0.20≤x≤0.95 wherein.
4. according to each mixture among the claim 1-3, wherein 3.0≤y≤6.0.
5. according to each mixture among the claim 1-4, wherein M
1=K, M
2=Na, 0.20≤x≤0.95 and 3.0≤y≤6.0.
6. according to each mixture among the claim 1-5, wherein M
1=K, M
2=Na, 0.50≤x≤0.90 and y=4.0,5.0 or 6.0.
7. method for preparing according to each mixture among the claim 1-6, it is included in protective gas or under reduced pressure, with corresponding alkali metalsulphide and sulphur heating or adding sulphur or do not adding under the sulphur corresponding alkali metals polysulfide heating.
8. method for preparing according to each mixture among the claim 1-6, it comprises reacts the corresponding basic metal and the sulphur that are in the liquefied ammonia under protective gas.
According to each mixture among the claim 1-6 as conducting heat or the purposes of thermal storage fluid.
10. one kind conducts heat or thermal storage fluid, and it comprises according to each mixture among the claim 1-6.
11. the alkali metals polysulfide of a following general formula and the mixture of alkali metal thiocyanate:
((M
1 xM
2 (1–x))
2S
y)
m(M
3 zM
4 (1–z)SCN)
(1–m)
M wherein
1, M
2, M
3, M
4=Li, Na, K, Rb, Cs, and M
1Be different from M
2, M
3Be different from M
4, 0.05≤x≤1,0.05≤z≤1,2.0≤y≤6.0 and m are molar ratio, wherein 0.05≤m≤0.95.
12. according to the mixture of claim 11, wherein M
1And M
3=K, and M
2And M
4=Na.
13. according to the mixture of claim 11 or 12,0.20≤x≤1 wherein.
14. according to each mixture among the claim 11-13, wherein 3.0≤y≤6.0.
15. according to each mixture among the claim 11-14, wherein 0.20≤z≤1.
16. according to each mixture among the claim 11-15, wherein 0.20≤m≤0.80.
17. according to each mixture among the claim 11-15, wherein M
1And M
3=K, M
2And M
4=Na, 0.20≤x≤1,0.20≤z≤0.95,3.0≤y≤6.0 and 0.20≤m≤0.95.
18. according to each mixture among the claim 11-16, wherein M
1And M
3=K, M
2And M
4=Na, 0.50≤x≤1,0.50≤z≤0.95, y=4.0,5.0 or 6.0 and 0.33≤m≤0.80.
19. a method for preparing according to each mixture among the claim 11-18, it comprises melts corresponding alkali metals polysulfide and alkali metal thiocyanate congruent melting.
20. according to each mixture among the claim 11-18 as conducting heat or the purposes of thermal storage fluid.
21. one kind conducts heat or thermal storage fluid, it comprises according to each mixture among the claim 11-18.
22. consist of (K
(1-x)Na
x)
2S
zThe alkali metals polysulfide mixture, wherein x=0-1 and z=2.3-3.5.
23. according to the mixture of claim 22 as conducting heat or the purposes of thermal storage fluid.
24. one kind conducts heat or thermal storage fluid, it comprises the mixture according to claim 22.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102010004063.0 | 2010-01-05 | ||
| DE102010004063 | 2010-01-05 | ||
| EP10154392 | 2010-02-23 | ||
| EP10154392.4 | 2010-02-23 | ||
| PCT/EP2010/070617 WO2011083054A1 (en) | 2010-01-05 | 2010-12-23 | Mixtures of alkali polysulfides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102712474A true CN102712474A (en) | 2012-10-03 |
Family
ID=43500011
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010800606647A Pending CN102712474A (en) | 2010-01-05 | 2010-12-23 | Mixtures of alkali polysulfides |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP2521692A1 (en) |
| JP (1) | JP2013516531A (en) |
| KR (1) | KR20120104423A (en) |
| CN (1) | CN102712474A (en) |
| AU (1) | AU2010340924A1 (en) |
| BR (1) | BR112012016656A2 (en) |
| CA (1) | CA2785174A1 (en) |
| CL (1) | CL2012001795A1 (en) |
| IL (1) | IL220543A0 (en) |
| MA (1) | MA33949B1 (en) |
| MX (1) | MX2012007392A (en) |
| TN (1) | TN2012000337A1 (en) |
| WO (1) | WO2011083054A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102884154A (en) * | 2010-04-09 | 2013-01-16 | 巴斯夫欧洲公司 | Liquid sulfur with improved viscosity as a heat transfer medium |
| CN110446681A (en) * | 2016-05-19 | 2019-11-12 | 纪尧姆·兰伯特 | Sulfide electrolyte for metal processing and extracting |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8679668B2 (en) | 2010-06-22 | 2014-03-25 | Basf Se | Industrial apparatus for the large-scale storage of electric energy |
| US8933262B2 (en) | 2011-05-24 | 2015-01-13 | Basf Se | Process for preparing polyisocyanates from biomass |
| US20130330634A1 (en) | 2012-06-11 | 2013-12-12 | Basf Se | Electrode unit |
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| US2697051A (en) * | 1952-09-17 | 1954-12-14 | Nat Lead Co | Treatment of titanium metal surfaces |
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| US5037552A (en) * | 1988-07-25 | 1991-08-06 | Jcg Corporation | Process for removal of mercury from a liquid hydrocarbon |
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| US2077856A (en) * | 1935-04-01 | 1937-04-20 | Rohm Otto | Method for producing stable alkali polysulphides |
| GB736750A (en) * | 1952-09-17 | 1955-09-14 | Nat Lead Co | Improvements in or relating to the treatment of titanium metal surfaces |
| US4335578A (en) | 1980-05-30 | 1982-06-22 | Ford Aerospace & Communications Corporation | Solar power converter with pool boiling receiver and integral heat exchanger |
| DE3436698C1 (en) | 1984-10-06 | 1986-05-22 | Degussa Ag, 6000 Frankfurt | Process for the production of sodium polysulfides from the elements sodium and sulfur |
| DE3824517A1 (en) | 1988-07-20 | 1990-01-25 | Bayer Ag | Heat transfer medium |
| JP2887694B2 (en) * | 1990-04-16 | 1999-04-26 | 日揮株式会社 | Method for removing mercury from liquid hydrocarbons |
| HU225602B1 (en) | 2004-01-26 | 2007-05-02 | Solar Technologia Es Vegyi Any | Method for extraction of thermal energy from solar collector and absorber therefore |
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2010
- 2010-12-23 JP JP2012547484A patent/JP2013516531A/en not_active Withdrawn
- 2010-12-23 MX MX2012007392A patent/MX2012007392A/en unknown
- 2010-12-23 WO PCT/EP2010/070617 patent/WO2011083054A1/en active Application Filing
- 2010-12-23 CN CN2010800606647A patent/CN102712474A/en active Pending
- 2010-12-23 MA MA35098A patent/MA33949B1/en unknown
- 2010-12-23 CA CA2785174A patent/CA2785174A1/en not_active Abandoned
- 2010-12-23 AU AU2010340924A patent/AU2010340924A1/en not_active Abandoned
- 2010-12-23 BR BR112012016656-5A patent/BR112012016656A2/en not_active IP Right Cessation
- 2010-12-23 EP EP10795730A patent/EP2521692A1/en not_active Withdrawn
- 2010-12-23 KR KR1020127020658A patent/KR20120104423A/en not_active Application Discontinuation
-
2012
- 2012-06-21 IL IL220543A patent/IL220543A0/en unknown
- 2012-06-27 TN TNP2012000337A patent/TN2012000337A1/en unknown
- 2012-07-03 CL CL2012001795A patent/CL2012001795A1/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2020661A (en) * | 1923-06-20 | 1935-11-12 | Phillips Petroleum Co | Process for treating hydrocarbon oils |
| US2697051A (en) * | 1952-09-17 | 1954-12-14 | Nat Lead Co | Treatment of titanium metal surfaces |
| US3296224A (en) * | 1963-03-29 | 1967-01-03 | Koppers Co Inc | Polybenzothiazole preparation |
| US5037552A (en) * | 1988-07-25 | 1991-08-06 | Jcg Corporation | Process for removal of mercury from a liquid hydrocarbon |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102884154A (en) * | 2010-04-09 | 2013-01-16 | 巴斯夫欧洲公司 | Liquid sulfur with improved viscosity as a heat transfer medium |
| CN102884154B (en) * | 2010-04-09 | 2016-04-13 | 巴斯夫欧洲公司 | As the fluid sulphur with improvement viscosity of heat-transfer medium |
| CN110446681A (en) * | 2016-05-19 | 2019-11-12 | 纪尧姆·兰伯特 | Sulfide electrolyte for metal processing and extracting |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2013516531A (en) | 2013-05-13 |
| WO2011083054A1 (en) | 2011-07-14 |
| IL220543A0 (en) | 2012-08-30 |
| BR112012016656A2 (en) | 2018-05-15 |
| AU2010340924A1 (en) | 2012-08-30 |
| EP2521692A1 (en) | 2012-11-14 |
| CL2012001795A1 (en) | 2012-10-12 |
| MX2012007392A (en) | 2012-08-23 |
| CA2785174A1 (en) | 2011-07-14 |
| TN2012000337A1 (en) | 2013-12-12 |
| MA33949B1 (en) | 2013-01-02 |
| KR20120104423A (en) | 2012-09-20 |
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Application publication date: 20121003 |