阅读说明：本技术 一种化学物质掺杂硫化锌的改性制备方法 (Modification preparation method of chemical substance doped zinc sulfide ) 是由 卢鹏荐 张威 于 2020-12-28 设计创作，主要内容包括：本发明公开了一种化学物质掺杂硫化锌的改性制备方法,具体涉及硫化锌制备技术领域,通过将摩尔比为2:1.5的硫磺、1,2-双(二苯基膦)乙烷导入反应釜中,通过不断的搅拌,同时加入芳香族化合物,进行再度搅拌,通过将反应釜内部通过加入氢气,随后使其反应后制取硫化氢,随后通过将1：5＝锌盐：水的质量比例配比,在之后的硫化氢注入锌盐溶液中的过程中通过加入质量份数为百分之二十的硫化铵溶液,随后获得硫化锌,其在加入硫化铵溶液前内部则已经开始进行稳定的产生硫化锌沉淀物,通过加入硫化铵后能够保持硫化锌在制取过程中,其锌盐溶液与硫化氢气体之间反应保持充分,使其在制取中不会出现反应不充分所造成的浪费问题。(The invention discloses a modification preparation method of chemical substance doped zinc sulfide, and particularly relates to the technical field of zinc sulfide preparation, wherein sulfur and 1, 2-bis (diphenylphosphino) ethane with a molar ratio of 2:1.5 are introduced into a reaction kettle, and are continuously stirred, aromatic compounds are added at the same time, and are stirred again, hydrogen is added into the reaction kettle, and then the hydrogen sulfide is prepared after the reaction, and then the reaction is carried out by adding 1: 5-zinc salt: the mass ratio of water is proportioned, in the process of injecting the hydrogen sulfide into the zinc salt solution, twenty percent of ammonium sulfide solution is added, then zinc sulfide is obtained, the inner part of the zinc sulfide solution starts to generate zinc sulfide precipitate stably before the ammonium sulfide solution is added, the zinc sulfide can be kept fully reacted with hydrogen sulfide gas in the preparation process after the ammonium sulfide is added, and the waste problem caused by insufficient reaction can not occur in the preparation process.)

1. A modification preparation method of chemical substance doped zinc sulfide comprises the following steps:

a. introducing sulfur and 1, 2-bis (diphenylphosphino) ethane with a molar ratio of 2:1.5 into a reaction kettle, continuously stirring, keeping the temperature at fifty ℃ in coordination, keeping the stirring time for 30min, simultaneously adding an aromatic compound, stirring again, keeping the mixture mixed for 20min, keeping the pressure at 0.1-0.2mpa, standing for a period of time, adding hydrogen into the reaction kettle, reacting to prepare hydrogen sulfide, and purifying the hydrogen sulfide gas and storing for later use;

b. followed by a reaction of 1: 5-zinc salt: proportioning the water according to the mass ratio, fully stirring the water for 10-15min, adding a proper amount of 1-nitroso and 6-sodium disulfonate while stirring until the stirring is finished to prepare a proper amount of zinc salt solution, purifying the zinc salt solution in an ion exchange mode, and storing the zinc salt solution;

c. and then, putting the prepared hydrogen sulfide gas into a zinc salt solution, adding the gas to start to generate partial precipitates, adding an ammonium sulfide solution with twenty percent of mass into the gas after the precipitation time is over 20min, then separating the precipitates from the rest solution to obtain zinc sulfide, and specifically purifying the zinc sulfide in subsequent use according to the specific use direction of the zinc sulfide.

2. The method for preparing the chemical substance doped zinc sulfide in the modified mode according to claim 1, is characterized in that: and separating the precipitate in the zinc salt solution by adopting filter pressing equipment after the precipitate is physically screened.

3. The method for preparing the chemical substance doped zinc sulfide in the modified mode according to claim 1, is characterized in that: the extracted finished zinc sulfide is dried at a temperature of about one hundred degrees centigrade and then roasted for 60min at a temperature ranging from seven hundred thirty degrees centigrade to seven hundred fifty degrees centigrade to keep the zinc sulfide fully dispersed.

4. The method for preparing the chemical substance doped zinc sulfide in the modified mode according to claim 1, is characterized in that: the internal pressure during the mixing of the zinc salt and water needs to be maintained to 0.1-0.2mpa during 2min while the temperature is maintained in the temperature range of forty to fifty degrees celsius.

5. The method for preparing the chemical substance doped zinc sulfide in the modified mode according to claim 1, is characterized in that: the standing time of the solution compounded by the sulfur, the 1, 2-bis (diphenylphosphino) ethane and the aromatic compound is 30 min.

Technical Field

The invention relates to the technical field of zinc sulfide preparation, in particular to a modification preparation method of chemical substance doped zinc sulfide.

Background

White to off-white or light yellow powder. The color of the visible light becomes dark. Is stable in dry air, and is gradually oxidized into zinc sulfate when being placed in wet air for a long time or containing water. Being soluble in dilute inorganic acids, soluble in bases, insoluble in water and irritant, zinc sulfide nanomaterials have attracted considerable attention as an important di-, hexa-compound semiconductor not only because of its excellent physical properties such as wide energy band gap, high refractive index, high light transmittance in the visible range, but also its great potential for applications in optical, electronic and optoelectronic devices. The zinc sulfide has excellent fluorescence effect and electroluminescence function, and the nano zinc sulfide has unique photoelectric effect and presents a plurality of excellent performances in the fields of electricity, magnetism, optics, mechanics, catalysis and the like, so the research of the nano zinc sulfide draws more attention, and the chemical formula of the zinc sulfide is ZnS. The chemical bond property between Zn and S is biased to covalent bond type. The crystals have 3 different configurations: the low temperature type, namely a sphalerite structure, exists in large quantity in the natural world, is colorless cubic crystal, has the coordination numbers of Zn and S of 4 and the relative density of 4.10, and is converted into the high temperature type at 1020 ℃; the high-temperature type, namely a wurtzite structure, colorless hexagonal crystals, Zn and S coordination numbers of 4, relative density of 3.98, melting point of about 1700 ℃, is a zinc sulfide high-temperature stable structure; the high pressure type, i.e., sodium chloride structure, Zn and S coordination numbers were all 6, the relative density was 5.21, and the aqueous compound ZnS. H2O was a white powder, the relative density was 3.98, and the melting point was 1049 ℃. The existing zinc sulfide extraction method has various ways, however, the existing zinc salt solution and hydrogen sulfide are mostly prepared by matching, the direct preparation reaction is insufficient, and certain waste exists.

Disclosure of Invention

In order to overcome the defects in the prior art, the invention provides a modification preparation method of chemical substance doped zinc sulfide, and the technical problems to be solved by the invention are that: the existing zinc sulfide extraction method has various ways, however, the existing zinc salt solution and hydrogen sulfide are mostly prepared by matching, the direct preparation reaction is insufficient, and the problem of certain waste exists.

In order to achieve the purpose, the invention provides the following technical scheme: a modification preparation method of chemical substance doped zinc sulfide comprises the following steps:

a. introducing sulfur and 1, 2-bis (diphenylphosphino) ethane with a molar ratio of 2:1.5 into a reaction kettle, continuously stirring, keeping the temperature at fifty ℃ in coordination, keeping the stirring time for 30min, simultaneously adding an aromatic compound, stirring again, keeping the mixture mixed for 20min, keeping the pressure at 0.1-0.2mpa, standing for a period of time, adding hydrogen into the reaction kettle, reacting to prepare hydrogen sulfide, and purifying the hydrogen sulfide gas and storing for later use.

b. Followed by a reaction of 1: 5-zinc salt: proportioning the water according to the mass ratio, fully stirring the water for 10-15min, adding a proper amount of 1-nitroso and 6-sodium disulfonate while stirring until the stirring is finished to prepare a proper amount of zinc salt solution, purifying the zinc salt solution in an ion exchange mode, and storing the zinc salt solution.

c. And then, putting the prepared hydrogen sulfide gas into a zinc salt solution, adding the gas to start to generate partial precipitates, adding an ammonium sulfide solution with twenty percent of mass into the gas after the precipitation time is over 20min, then separating the precipitates from the rest solution to obtain zinc sulfide, and specifically purifying the zinc sulfide in subsequent use according to the specific use direction of the zinc sulfide.

As a further scheme of the invention: and separating the precipitate in the zinc salt solution by adopting filter pressing equipment after the precipitate is physically screened.

As a further scheme of the invention: the extracted finished zinc sulfide is dried at a temperature of about one hundred degrees centigrade and then roasted for 60min at a temperature ranging from seven hundred thirty degrees centigrade to seven hundred fifty degrees centigrade to keep the zinc sulfide fully dispersed.

As a further scheme of the invention: the internal pressure during the mixing of the zinc salt and water needs to be maintained to 0.1-0.2mpa during 2min while the temperature is maintained in the temperature range of forty to fifty degrees celsius.

As a further scheme of the invention: the standing time of the solution compounded by the sulfur, the 1, 2-bis (diphenylphosphino) ethane and the aromatic compound is 30 min.

The invention has the beneficial effects that:

the invention introduces sulfur and 1, 2-bis (diphenylphosphino) ethane with a molar ratio of 2:1.5 into a reaction kettle, continuously stirs while adding aromatic compounds, stirs again, prepares hydrogen sulfide by adding hydrogen into the reaction kettle and then reacting the hydrogen, and then prepares hydrogen sulfide by adding 1: 5-zinc salt: the method comprises the following steps of proportioning water according to a mass ratio, fully stirring the mixture, adding a proper amount of 1-nitroso and 6-sodium disulfonate while stirring the mixture until the stirring is completed to prepare a proper amount of zinc salt solution, adding twenty mass percent of ammonium sulfide solution in the process of injecting hydrogen sulfide into the zinc salt solution, and then obtaining zinc sulfide, wherein the zinc sulfide is already stably generated in the inner part before the ammonium sulfide solution is added, and the reaction between the zinc salt solution and hydrogen sulfide gas is fully maintained in the preparation process of the zinc sulfide after the ammonium sulfide is added, so that the waste problem caused by insufficient reaction can not be caused in the preparation process.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1:

a modification preparation method of chemical substance doped zinc sulfide comprises the following steps:

a. introducing sulfur and 1, 2-bis (diphenylphosphino) ethane with a molar ratio of 2:1.5 into a reaction kettle, continuously stirring, keeping the temperature at fifty ℃ in coordination, keeping the stirring time for 30min, simultaneously adding an aromatic compound, stirring again, keeping the mixture mixed for 20min, keeping the pressure at 0.1-0.2mpa, standing for a period of time, adding hydrogen into the reaction kettle, reacting to prepare hydrogen sulfide, and purifying the hydrogen sulfide gas and storing for later use.

b. Followed by a reaction of 1: 5-zinc salt: proportioning the water according to the mass ratio, fully stirring the water for 10-15min, adding a proper amount of 1-nitroso and 6-sodium disulfonate while stirring until the stirring is finished to prepare a proper amount of zinc salt solution, purifying the zinc salt solution in an ion exchange mode, and storing the zinc salt solution.

c. And then, putting the prepared hydrogen sulfide gas into a zinc salt solution, adding the gas to start to generate partial precipitates, adding an ammonium sulfide solution with twenty percent of mass into the gas after the precipitation time is over 20min, then separating the precipitates from the rest solution to obtain zinc sulfide, and specifically purifying the zinc sulfide in subsequent use according to the specific use direction of the zinc sulfide.

And separating the precipitate in the zinc salt solution by adopting filter pressing equipment after the precipitate is physically screened.

The extracted finished zinc sulfide is dried at a temperature of about one hundred degrees centigrade and then roasted for 60min at a temperature ranging from seven hundred thirty degrees centigrade to seven hundred fifty degrees centigrade to keep the zinc sulfide fully dispersed.

The internal pressure during the mixing of the zinc salt and water needs to be maintained to 0.1-0.2mpa during 2min while the temperature is maintained in the temperature range of forty to fifty degrees celsius.

The standing time of the solution compounded by the sulfur, the 1, 2-bis (diphenylphosphino) ethane and the aromatic compound is 30 min.

Example 2:

a. introducing sulfur and 1, 2-bis (diphenylphosphino) ethane with a molar ratio of 2:1.5 into a reaction kettle, continuously stirring, keeping the temperature at fifty ℃ in coordination, keeping the stirring time for 30min, simultaneously adding an aromatic compound, stirring again, keeping the mixture mixed for 20min, keeping the pressure at 0.1-0.2mpa, standing for a period of time, adding hydrogen into the reaction kettle, reacting to prepare hydrogen sulfide, and purifying the hydrogen sulfide gas and storing for later use.

b. Followed by a reaction of 1: 5-zinc salt: proportioning the water according to the mass ratio, fully stirring the water for 10-15min, adding a proper amount of 1-nitroso and 6-sodium disulfonate while stirring until the stirring is finished to prepare a proper amount of zinc salt solution, purifying the zinc salt solution in an ion exchange mode, and storing the zinc salt solution.

C. And then, putting the prepared hydrogen sulfide gas into a zinc salt solution, wherein the gas begins to generate partial precipitates, separating the precipitates from the rest solution after the precipitation time is over 20min to obtain zinc sulfide, and specifically purifying the zinc sulfide in the subsequent use according to the specific use direction of the zinc sulfide.

And separating the precipitate in the zinc salt solution by adopting filter pressing equipment after the precipitate is physically screened.

The extracted finished zinc sulfide is dried at a temperature of about one hundred degrees centigrade and then roasted for 60min at a temperature ranging from seven hundred thirty degrees centigrade to seven hundred fifty degrees centigrade to keep the zinc sulfide fully dispersed.

The internal pressure during the mixing of the zinc salt and water needs to be maintained to 0.1-0.2mpa during 2min while the temperature is maintained in the temperature range of forty to fifty degrees celsius.

The standing time of the solution compounded by the sulfur, the 1, 2-bis (diphenylphosphino) ethane and the aromatic compound is 30 min.

Example 3:

a. introducing sulfur and 1, 2-bis (diphenylphosphino) ethane with a molar ratio of 2:1.5 into a reaction kettle, continuously stirring, keeping the temperature at fifty ℃ in coordination, keeping the stirring time for 30min, simultaneously adding an aromatic compound, stirring again, keeping the mixture mixed for 20min, keeping the pressure at 0.1-0.2mpa, standing for a period of time, adding hydrogen into the reaction kettle, reacting to prepare hydrogen sulfide, and purifying the hydrogen sulfide gas and storing for later use.

b. Followed by a reaction of 1: 5-zinc salt: proportioning the water according to the mass ratio, fully stirring the water for 10-15min, adding a proper amount of 1-nitroso and 6-sodium disulfonate while stirring until the stirring is finished to prepare a proper amount of zinc salt solution, purifying the zinc salt solution in an ion exchange mode, and storing the zinc salt solution.

C. And then, putting the prepared hydrogen sulfide gas into a zinc salt solution, adding twenty percent of ammonium sulfide solution into the gas when the gas begins to generate partial precipitates, then separating the precipitates from the rest solution to obtain zinc sulfide, and specifically purifying the zinc sulfide in the subsequent use according to the specific use direction of the zinc sulfide.

And separating the precipitate in the zinc salt solution by adopting filter pressing equipment after the precipitate is physically screened.

The extracted finished zinc sulfide is dried at a temperature of about one hundred degrees centigrade and then roasted for 60min at a temperature ranging from seven hundred thirty degrees centigrade to seven hundred fifty degrees centigrade to keep the zinc sulfide fully dispersed.

The internal pressure during the mixing of the zinc salt and water needs to be maintained to 0.1-0.2mpa during 2min while the temperature is maintained in the temperature range of forty to fifty degrees celsius.

The standing time of the solution compounded by the sulfur, the 1, 2-bis (diphenylphosphino) ethane and the aromatic compound is 30 min.

Example 4:

a. introducing sulfur and 1, 2-bis (diphenylphosphino) ethane with a molar ratio of 2:1.5 into a reaction kettle, continuously stirring, keeping the temperature at fifty ℃ in coordination, keeping the stirring time for 30min, simultaneously adding an aromatic compound, stirring again, keeping the mixture mixed for 20min, standing for a period of time, adding hydrogen into the reaction kettle, reacting to prepare hydrogen sulfide, and purifying the hydrogen sulfide gas and storing for later use.

b. Followed by a reaction of 1: 5-zinc salt: proportioning the water according to the mass ratio, fully stirring the water for 10-15min, adding a proper amount of 1-nitroso and 6-sodium disulfonate while stirring until the stirring is finished to prepare a proper amount of zinc salt solution, purifying the zinc salt solution in an ion exchange mode, and storing the zinc salt solution.

c. And then, putting the prepared hydrogen sulfide gas into a zinc salt solution, adding the gas to start to generate partial precipitates, adding an ammonium sulfide solution with twenty percent of mass into the gas after the precipitation time is over 20min, then separating the precipitates from the rest solution to obtain zinc sulfide, and specifically purifying the zinc sulfide in subsequent use according to the specific use direction of the zinc sulfide.

And separating the precipitate in the zinc salt solution by adopting filter pressing equipment after the precipitate is physically screened.

The extracted finished zinc sulfide is dried at a temperature of about one hundred degrees centigrade and then roasted for 60min at a temperature ranging from seven hundred thirty degrees centigrade to seven hundred fifty degrees centigrade to keep the zinc sulfide fully dispersed.

The internal pressure during the mixing of the zinc salt and water needs to be maintained to 0.1-0.2mpa during 2min while the temperature is maintained in the temperature range of forty to fifty degrees celsius.

The standing time of the solution compounded by the sulfur, the 1, 2-bis (diphenylphosphino) ethane and the aromatic compound is 30 min.

The following table is obtained according to examples 1 to 4:

	precipitating for 20min	Ammonium sulfide	Pressure of	Effect of reaction
					Example 1	Precipitation of	Adding into	0.1-0.2mpa	Complete reaction
Example 2	Precipitation of	Is not added	0.1-0.2mpa	Has residues
					Example 3	Does not precipitate	Adding into	0.1-0.2mpa	Complete reaction
Example 4	Precipitation of	Adding into	0.5-0.15mpa	Complete reaction

In conclusion, the present invention: in the process of generating zinc sulfide by the reaction between the zinc salt solution and the hydrogen sulfide gas, the addition of the ammonium sulfide directly influences whether the hydrogen sulfide gas can fully react with the zinc salt solution.

A modification preparation method of chemical substance doped zinc sulfide comprises the following steps:

s1, introducing sulfur and 1, 2-bis (diphenylphosphino) ethane in a molar ratio of 2:1.5 into a reaction kettle, continuously stirring, keeping the temperature at fifty ℃ in coordination, keeping the stirring time for 30min, adding an aromatic compound, stirring again, keeping the mixture mixed for 20min, keeping the pressure at 0.1-0.2mpa, standing for a period of time, adding hydrogen into the reaction kettle, reacting to prepare hydrogen sulfide, purifying the hydrogen sulfide gas, and storing for later use.

S2, followed by converting 1: 5-zinc salt: proportioning the water according to the mass ratio, fully stirring the water for 10-15min, adding a proper amount of 1-nitroso and 6-sodium disulfonate while stirring until the stirring is finished to prepare a proper amount of zinc salt solution, purifying the zinc salt solution in an ion exchange mode, and storing the zinc salt solution.

S3, then, the prepared hydrogen sulfide gas is placed in the zinc salt solution, the gas begins to generate partial precipitates, after 20min of precipitation time, the ammonium sulfide solution with the mass percentage of twenty percent is added into the gas, then, the precipitates are separated from the rest solution to obtain the zinc sulfide, and in the subsequent use, the zinc sulfide is specifically purified according to the specific use direction of the zinc sulfide.

S4, separating the precipitate in the zinc salt solution by using filter pressing equipment after physical screening, drying the extracted finished product zinc sulfide at a temperature of about one hundred ℃, roasting at a temperature of between seven hundred thirty ℃ and seven hundred fifty ℃ for 60min to keep the zinc sulfide fully dispersed, wherein the internal pressure needs to be kept to 0.1-0.2mpa within 2min in the mixing process of the zinc salt and water, and the temperature is kept to be between forty ℃ and fifty ℃ at the same time, and the standing time of the solution matched among the sulfur, the 1, 2-bis (diphenylphosphine) ethane and the aromatic compound is specifically 30 min.

Hydrogen sulfide is prepared by introducing sulfur and 1, 2-bis (diphenylphosphino) ethane in a molar ratio of 2:1.5 into a reaction vessel, stirring again by continuous stirring while adding an aromatic compound, by introducing hydrogen gas into the reaction vessel and then reacting them, and then by introducing 1: 5-zinc salt: the method comprises the following steps of proportioning water according to a mass ratio, fully stirring the mixture, adding a proper amount of 1-nitroso and 6-sodium disulfonate while stirring the mixture until the stirring is completed to prepare a proper amount of zinc salt solution, adding twenty mass percent of ammonium sulfide solution in the process of injecting hydrogen sulfide into the zinc salt solution, and then obtaining zinc sulfide, wherein the zinc sulfide is already stably generated in the inner part before the ammonium sulfide solution is added, and the reaction between the zinc salt solution and hydrogen sulfide gas is fully maintained in the preparation process of the zinc sulfide after the ammonium sulfide is added, so that the waste problem caused by insufficient reaction can not be caused in the preparation process.

The points to be finally explained are: although the present invention has been described in detail with reference to the general description and the specific embodiments, on the basis of the present invention, the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.