阅读说明：本技术 三聚氯氰的生产工艺 (Process for producing cyanuric chloride ) 是由 刘子程 李洪刚 黄明辉 华亮 尹诗 马传懿 丛之皓 栾浩 陈英会 孙颖 于 2021-08-03 设计创作，主要内容包括：本发明公开了三聚氯氰的生产工艺,包括三聚氯氰车间一至四工段生产工艺流程、三聚氯氰车间五工段生产工艺流程,其中包括一种导热油及其制备方法。本发明所得到的导热油具有导热能力强、酸值低、热稳定性好的优点,将其应用于三聚氯氰的生产中可以增强生产工艺的可靠性。(The invention discloses a production process of cyanuric chloride, which comprises a production process flow of one to four sections of a cyanuric chloride workshop and a production process flow of five sections of the cyanuric chloride workshop, wherein the production process flow comprises heat conduction oil and a preparation method thereof. The heat conduction oil obtained by the invention has the advantages of strong heat conduction capability, low acid value and good thermal stability, and the reliability of the production process can be enhanced when the heat conduction oil is applied to the production of cyanuric chloride.)

1. A preparation method of heat conduction oil is characterized by comprising the following steps: and mixing the base oil, the heat-conducting filler, the antioxidant and the passivator, and then homogenizing to obtain the heat-conducting oil.

2. The method for preparing conduction oil according to claim 1, characterized in that: the antioxidant is one or a mixture of 3, 3-dithiodipropionic acid di (N-succinimide) ester, 3' -dithiodipropionic acid dimethyl ester and thiopropionic acid furfuryl ester.

3. The method for preparing conduction oil according to claim 1, characterized in that: the passivating agent is one or a mixture of two of N, N '-bis (o-hydroxybenzylidene) -1, 2-diaminopropane and N, N' -disalicylic acid water ester-1, 3-diaminopropane.

4. The method for preparing heat transfer oil according to claim 1, wherein the method for preparing the heat transfer filler comprises the following steps:

j1 mixing the heat-conducting inorganic substance uniformly by a planetary ball mill through a wet grinding method, and then drying to obtain mixed powder;

j2 mixing the cross-linking agent, long carbon chain ester and methanol and homogenizing to obtain emulsion A;

j3 mixing and stirring the mixed powder, the emulsion A and the synergist, standing, and taking bottom sediment to obtain the heat-conducting filler.

5. The method for preparing conduction oil according to claim 4, characterized in that: the synergist is 1, 8-naphthalic anhydride and/or phthalic anhydride.

6. A kind of heat conduction oil, its characteristic lies in: the method for preparing heat transfer oil according to any one of claims 1 to 5.

7. The production process of cyanuric chloride is characterized in that: the method comprises a production process flow of one to four sections of a cyanuric chloride workshop and a production process flow of five sections of the cyanuric chloride workshop, wherein the production process flow of the one to four sections of the cyanuric chloride workshop and the production process flow of the five sections of the cyanuric chloride workshop comprise the heat conducting oil in claim 6.

8. The process for producing cyanuric chloride as claimed in claim 7, wherein the process flow for the production of cyanuric chloride in one to four stages of the cyanuric chloride plant comprises the following steps:

(1) feeding the liquid chlorine from the liquid chlorine storage tank into a gasification device to obtain chlorine; the obtained chlorine gas enters a buffer tank;

(2) pumping the NaCN aqueous solution from the storage tank to a batching tank, and diluting with water for later use;

(3) introducing chlorine and the diluted NaCN aqueous solution obtained in the step (2) into the reactor, and starting chlorination reaction;

(4) the chlorinated product cyanogen chloride gas rises in the reactor and is cooled after passing through a primary cooler and a secondary cooler;

(5) the cyanogen chloride gas after temperature reduction is further dewatered by a drier after entrained water mist is removed by a water mist catcher; the water mist catcher intercepts water, then reaches the top of the reactor and then flows back to the reactor;

(6) waste water from the bottom of the reactor enters a desorption kettle, is heated to 75-80 ℃ to gasify cyanogen chloride in a liquid phase and is recovered; the resolved liquid phase is the chlorination wastewater which is sent to a reclaimed water workshop for purification and reuse;

(7) in the drying procedure, blocky calcium chloride is filled in the drying tower, and when cyanogen chloride gas passes through a blocky calcium chloride layer, the entrained residual moisture is trapped in the blocky calcium chloride; after absorbing water, the blocky calcium chloride in the drying tower becomes a calcium chloride liquid saturated solution which contains hydrochloric acid and is neutralized and purified by quicklime;

(8) the dried cyanogen chloride gas enters a polymerization furnace and is polymerized into cyanuric chloride at high temperature under the action of a catalyst; the heat conducting oil of claim 6 is adopted in a polymerization furnace to remove polymerization heat and keep the polymerization temperature stable;

(9) the gaseous cyanuric chloride is discharged from a polymerization furnace and enters a crystallizer to meet with dry cold air, and the gaseous cyanuric chloride is desublimated into a powdery solid product;

(10) unreacted chlorine gas, unpolymerized cyanogen chloride and uncrystallized cyanuric chloride gas pass through a trap and a catching bin and enter a tail gas treatment system along with air; the tail gas tower I spray liquid is sodium hydroxide aqueous solution, and sodium hypochlorite is generated after chlorine is absorbed; the second tower spraying liquid is water and absorbs residual chlorine;

(11) the qualified tail gas after treatment is discharged in high altitude through an exhaust chimney;

(12) the ventilation and exhaust in the workshop is treated by the sodium hydroxide aqueous solution in the environmental protection tower and then is concentrated to the discharge port of the tail gas system for uniform discharge, and the sodium hydroxide aqueous solution sprayed by the environmental protection tower is sent to the tail gas spraying tower for continuous use.

9. The production process of cyanuric chloride as claimed in claim 7, wherein the production process flow of the five sections of the cyanuric chloride workshop consists of the following steps:

s1, feeding the liquid chlorine from the liquid chlorine storage tank into a gasification device to obtain chlorine; the obtained chlorine gas enters a buffer tank and is ready to enter a reactor;

s2, pumping the NaCN aqueous solution from the storage tank to a batching tank, and diluting the NaCN aqueous solution with water for later use;

introducing chlorine gas and the diluted NaCN aqueous solution obtained in the step S2 into the S3 reactor, and starting chlorination reaction;

circulating reaction liquid in the S4 reactor outside and cooling to keep the temperature in the reactor unchanged;

s5 Chlorination product cyanogen chloride gas rises in the reactor, passes through the exchange tower to be in countercurrent contact with water from top to bottom, and the unreacted chlorine gas is intercepted back to the reactor

S6, allowing the cyanogen chloride gas to pass through the exchange tower to continuously rise, cooling the cyanogen chloride gas in a cooler at the top of the tower, and returning condensed water to the reactor;

the cyanogen chloride gas after the temperature reduction of S7 is further dewatered by a drier after the entrained water mist is removed by a water mist catcher; the water mist catcher intercepts water, then reaches the top of the reactor and then flows back to the reactor;

when the temperature of the external circulation of the S8 reactor is reduced, a part of the flow is diverted to a resolving kettle, and cyanogen chloride in the liquid phase is gasified and recovered by heating; the resolved liquid phase is the chlorination wastewater which is sent to a reclaimed water workshop for purification and reuse;

s9, in the drying process, calcium sulfate particles are filled in a drying tower, and when cyanogen chloride gas passes through a calcium sulfate particle layer, residual moisture carried by the cyanogen chloride gas is intercepted in the calcium sulfate particle particles; when the calcium sulfate particles in one drying tower absorb water, the other drying tower is switched to work, and the switched tower is subjected to hot air regeneration to remove adsorbed water for later use;

s10, the dried cyanogen chloride gas enters a polymerization furnace, and is polymerized into cyanuric chloride at high temperature under the action of a catalyst; the heat conducting oil of claim 6 is adopted in a polymerization furnace to remove polymerization heat and keep the polymerization temperature stable;

s11 allowing cyanuric chloride to flow out of the polymerization furnace and enter a crystallizer, and meeting with dry cold air to desublimate into a powdery solid product;

s12, passing unreacted chlorine, unpolymerized cyanogen chloride and uncrystallized cyanuric chloride gas through a trap and a catching bin, and entering a tail gas treatment system along with air; the tail gas tower I spray liquid is sodium hydroxide aqueous solution, and sodium hypochlorite is generated after chlorine is absorbed; the second tower spraying liquid is water and absorbs residual chlorine; the qualified tail gas after treatment is discharged in high altitude through an exhaust chimney;

and the waste gas generated by the regeneration of the S13 calcium sulfate desiccant hot air is treated by the sodium hydroxide aqueous solution of the spray tower and then is concentrated to the discharge port of the tail gas system for uniform discharge.

10. A process for the production of cyanuric chloride as claimed in any of claims 8 to 9, wherein: the catalyst is activated carbon and/or molybdenum disulfide.

Technical Field

The invention relates to the technical field of cyanuric chloride, in particular to a production process of cyanuric chloride.

Background

Cyanuric chloride, an important chemical intermediate, has been widely used in various chemical fields today, and is one of the important raw materials for pesticides, herbicides, reactive dyes and fluorescent whitening agents. Furthermore, cyanuric chloride is also useful in the production of nitrogen fertilizer synergists, surfactants, plasticizers, stabilizers, rubber vulcanization accelerators, polymer blowing agents, resin fixatives, polymerization catalysts, fire retardants, photographic sensitizers, adhesives, cyanoaldehydes, reverse osmosis membranes, stability propellants and a variety of pharmaceuticals.

The heat conducting oil is a working medium for transferring heat. The heat conducting oil on the market meets the requirements of uniform heating, accurate temperature adjustment and control, capability of generating high temperature under low steam pressure, good heat transfer effect, energy conservation, convenient transportation and operation and the like. In recent years, various complex systems of heat transfer oil have been widely used in various applications. The heat transfer oils on the market are mainly classified into two types, i.e., mineral type heat transfer oils and synthetic type heat transfer oils. The mineral heat conducting oil is obtained by mixing base oil produced by crude oil through the working procedures of catalytic cracking, atmospheric distillation, reduced pressure distillation, dewaxing, refining and the like as a raw material with an auxiliary agent. Because the base oil is wide and easy to obtain, the mineral type heat conduction oil prepared from the base oil is low in price, but the mineral type heat conduction oil is low in use temperature and poor in thermal stability, and the base oil can be subjected to reactions such as oxidation, thermal cracking, thermal polymerization and the like along with the prolonging of the use time, so that the use performance of the heat conduction oil is influenced, and the service life of the heat conduction oil is shortened; the synthetic heat transfer oil comprises biphenyl and biphenyl ether type heat transfer oil, monobenzyltoluene and dibenzyltoluene type heat transfer oil, and the biphenyl and biphenyl ether type heat transfer oil can generate phenolic substances in the using process, so that the container is easily damaged, and potential safety hazards are brought. The heat conducting oil of the monobenzyltoluene and the dibenzyltoluene type has good thermal stability and safe use, but the preparation cost of the monobenzyltoluene and the dibenzyltoluene is higher, and the economic burden is brought to manufacturers for production and use.

At present, the prior art still lacks a heat conduction oil with high heat conductivity, low acid value, oxidation resistance and good thermal stability.

Patent CN106479448A provides a heat conducting oil and a method for preparing the heat conducting oil, which is composed of base oil, a high-temperature antioxidant, a viscosity regulator, a metal passivator and an anti-scaling agent, but the heat conducting ability is poor, which fails to meet increasingly severe market demands, and the technical problem of low acid value is not realized, and the problem of low thermal stability of the heat conducting oil in the prior art is not solved.

Disclosure of Invention

Aiming at the defects in the prior art, the invention provides a production process of cyanuric chloride.

In order to solve the technical problems, the invention adopts the technical scheme that:

the production process of cyanuric chloride comprises a high-temperature chlorination method and a low-temperature chlorination method.

The high-temperature chlorination method adopts a production process flow from one to four work sections in a cyanuric chloride workshop;

the production process flow (high-temperature chlorination method) of one to four sections of the cyanuric chloride workshop comprises the following steps:

(1) feeding the liquid chlorine from the liquid chlorine storage tank into a gasification device to obtain chlorine; the obtained chlorine gas enters a buffer tank;

(2) pumping the NaCN aqueous solution from the storage tank to a batching tank, and diluting with water for later use;

(3) introducing chlorine and the diluted NaCN aqueous solution obtained in the step (2) into the reactor, and starting chlorination reaction;

(4) the chlorinated product cyanogen chloride gas rises in the reactor and is cooled after passing through a primary cooler and a secondary cooler;

(5) the cyanogen chloride gas after temperature reduction is further dewatered by a drier after entrained water mist is removed by a water mist catcher; the water mist catcher intercepts water, then reaches the top of the reactor and then flows back to the reactor;

(6) waste water from the bottom of the reactor enters a desorption kettle, is heated to 75-80 ℃ to gasify cyanogen chloride in a liquid phase and is recovered; the resolved liquid phase is the chlorination wastewater which is sent to a reclaimed water workshop for purification and reuse;

(7) in the drying procedure, blocky calcium chloride is filled in the drying tower, and when cyanogen chloride gas passes through a blocky calcium chloride layer, the entrained residual moisture is trapped in the blocky calcium chloride; after absorbing water, the blocky calcium chloride in the drying tower becomes a calcium chloride liquid saturated solution which contains hydrochloric acid and is neutralized and purified by quicklime;

(8) the dried cyanogen chloride gas enters a polymerization furnace and is polymerized into cyanuric chloride at high temperature under the action of a catalyst; the polymerization furnace uses heat conducting oil to remove polymerization heat and keep the polymerization temperature stable; the catalyst is a mixture of activated carbon and molybdenum disulfide;

(9) the gaseous cyanuric chloride is discharged from a polymerization furnace and enters a crystallizer to meet with dry cold air, and the gaseous cyanuric chloride is desublimated into a powdery solid product;

(10) unreacted chlorine gas, unpolymerized cyanogen chloride and uncrystallized cyanuric chloride gas pass through a trap and a catching bin and enter a tail gas treatment system along with air; the tail gas tower I spray liquid is sodium hydroxide aqueous solution, and sodium hypochlorite is generated after chlorine is absorbed; the second tower spraying liquid is water and absorbs residual chlorine;

(11) the qualified tail gas after treatment is discharged in high altitude through an exhaust chimney;

(12) the ventilation and exhaust in the workshop is treated by the sodium hydroxide aqueous solution in the environmental protection tower and then is concentrated to the discharge port of the tail gas system for uniform discharge, and the sodium hydroxide aqueous solution sprayed by the environmental protection tower is sent to the tail gas spraying tower for continuous use.

In the production process of the cyanuric chloride, the molybdenum disulfide and the activated carbon are mixed to be used as the catalyst, so that the cyanuric chloride with higher quality is obtained.

The low-temperature chlorination method adopts a production process flow of five sections of a cyanuric chloride workshop;

the production process flow (low-temperature chlorination method) of the five sections of the cyanuric chloride workshop comprises the following steps:

s1, feeding the liquid chlorine from the liquid chlorine storage tank into a gasification device to obtain chlorine; the obtained chlorine gas enters a buffer tank;

s2, pumping the NaCN aqueous solution from the storage tank to a batching tank, and diluting the NaCN aqueous solution with water for later use;

introducing chlorine gas and the diluted NaCN aqueous solution obtained in the step S2 into the S3 reactor, and starting chlorination reaction;

circulating reaction liquid in the S4 reactor outside and cooling to keep the temperature in the reactor unchanged;

s5 the chlorinated product cyanogen chloride gas rises in the reactor, and is in countercurrent contact with water from top to bottom through an exchange tower, and unreacted chlorine gas is intercepted back to the reactor;

s6, allowing the cyanogen chloride gas to pass through the exchange tower to continuously rise, cooling in a tower top cooler (secondary cooling), and returning condensed water to the reactor;

the cyanogen chloride gas after the temperature reduction of S7 is further dewatered by a drier after the entrained water mist is removed by a water mist catcher; the water mist catcher intercepts water, then reaches the top of the reactor and then flows back to the reactor;

when the temperature of the external circulation of the S8 reactor is reduced, a part of the flow is diverted to a resolving kettle, and cyanogen chloride in the liquid phase is gasified and recovered by heating; the resolved liquid phase is the chlorination wastewater which is sent to a reclaimed water workshop for purification and reuse;

s9, in the drying process, calcium sulfate particles are filled in a drying tower, and when cyanogen chloride gas passes through a calcium sulfate particle layer, residual moisture carried by the cyanogen chloride gas is intercepted in the calcium sulfate particle particles; when the calcium sulfate particles in one drying tower absorb water, the other drying tower is switched to work, and the switched tower is subjected to hot air regeneration to remove adsorbed water for later use;

s10, the dried cyanogen chloride gas enters a polymerization furnace, and is polymerized into cyanuric chloride at high temperature under the action of a catalyst; the polymerization furnace uses heat conducting oil to remove polymerization heat and keep the polymerization temperature stable; the catalyst is a mixture of activated carbon and molybdenum disulfide;

s11 allowing cyanuric chloride to flow out of the polymerization furnace and enter a crystallizer, and meeting with dry cold air to desublimate into a powdery solid product;

s12, passing unreacted chlorine, unpolymerized cyanogen chloride and uncrystallized cyanuric chloride gas through a trap and a catching bin, and entering a tail gas treatment system along with air; the tail gas tower I spray liquid is sodium hydroxide aqueous solution, and sodium hypochlorite is generated after chlorine is absorbed; the second tower spraying liquid is water and absorbs residual chlorine;

and after being treated by a sodium hydroxide aqueous solution in a spray tower, the waste gas generated by the regeneration of S13 calcium sulfate hot air is concentrated to a discharge port of a tail gas system and is uniformly discharged.

As a preferable scheme, the production process flow (high-temperature chlorination method) of one to four sections of the cyanuric chloride workshop comprises the following steps:

(1) feeding the liquid chlorine from the liquid chlorine storage tank into a gasification device to obtain chlorine; the obtained chlorine gas enters a buffer tank; in the liquid chlorine storage tank, the working liquid level is 2/3, and the working pressure is 0.5-0.6 MPa; the temperature in the gasification device is 75-80 ℃, the air pressure is 0.75-0.85MPa, the gasification yield is 430-460kg/h, and the gasification outlet temperature is 15-20 ℃; the temperature in the buffer tank is 40-45 ℃, and the air pressure is 0.5-0.6 Mpa;

(2) pumping 25-30 wt.% NaCN aqueous solution from the storage tank to a batching tank, and diluting with water to a concentration of 12-20 wt.% for standby; the temperature of the storage tank is 18-20 ℃;

(3) introducing chlorine gas and the diluted NaCN aqueous solution obtained in the step (2) into the reactor, and starting chlorination reaction at 93-95 ℃; the volume ratio of the NaCN aqueous solution to the chlorine is 1 (1-1.02);

(4) the chlorinated product is cyanogen chloride gas; the cyanogen chloride gas rises in the reactor and is cooled to 10-15 ℃ after passing through a primary cooler and a secondary cooler; in the primary cooler, the temperature of the hydrogen chloride gas is reduced from 90-95 ℃ to 30-35 ℃; in the secondary cooler, the temperature of the hydrogen chloride gas is reduced from 30-35 ℃ to 10-15 ℃;

(5) the cyanogen chloride gas after temperature reduction is further dewatered by a drier after entrained water mist is removed by a water mist catcher; the water mist catcher intercepts water, then reaches the top of the reactor and then flows back to the reactor; the flow rate of the hydrogen chloride gas in the water mist catcher is 1000-1200L/h;

(6) waste water from the bottom of the reactor enters a desorption kettle, is heated to 75-80 ℃ to gasify cyanogen chloride in a liquid phase and is recovered; the resolved liquid phase is the chlorination wastewater which is sent to a reclaimed water workshop for purification and reuse;

(7) in the drying procedure, blocky calcium chloride is filled in the drying tower, and when cyanogen chloride gas passes through a blocky calcium chloride layer, the entrained residual moisture is trapped in the blocky calcium chloride; after absorbing water, the blocky calcium chloride in the drying tower becomes a calcium chloride liquid saturated solution which contains hydrochloric acid and is neutralized and purified by quicklime;

(8) the dried cyanogen chloride gas enters a polymerization furnace and is polymerized into cyanuric chloride at high temperature under the action of a catalyst; the polymerization furnace uses heat conducting oil to remove polymerization heat and keep the polymerization temperature stable; the catalyst is a mixture of activated carbon and molybdenum disulfide; the polymerization temperature is 370-380 ℃;

(9) the gaseous cyanuric chloride is discharged from a polymerization furnace and enters a crystallizer to meet with dry cold air, and the gaseous cyanuric chloride is desublimated into a powdery solid product; the temperature of the cold air is 4-6 ℃, and the flow rate is 500-600L/h;

(10) unreacted chlorine gas, unpolymerized cyanogen chloride and uncrystallized cyanuric chloride gas pass through a trap and a catching bin and enter a tail gas treatment system along with air; the tail gas tower I spray liquid is sodium hydroxide aqueous solution, and sodium hypochlorite is generated after chlorine is absorbed; the second tower spraying liquid is water and absorbs residual chlorine;

(11) the qualified tail gas after treatment is discharged at high altitude through an exhaust chimney with the height of 35-40 m;

(12) the ventilation and exhaust in the workshop is treated by the sodium hydroxide aqueous solution in the environmental protection tower and then is concentrated to the discharge port of the tail gas system for uniform discharge, and the sodium hydroxide aqueous solution sprayed by the environmental protection tower is sent to the tail gas spraying tower for continuous use.

As a preferable scheme, the production process flow (low-temperature chlorination method) of the five sections of the cyanuric chloride workshop comprises the following steps:

s1, feeding the liquid chlorine from the liquid chlorine storage tank into a gasification device to obtain chlorine; the obtained chlorine gas enters a buffer tank; in the liquid chlorine storage tank, the working liquid level is 2/3, and the working pressure is 0.5-0.6 MPa; the temperature in the gasification device is 75-80 ℃, the air pressure is 0.75-0.85MPa, the gasification yield is 430-460kg/h, and the gasification outlet temperature is 15-20 ℃; the temperature in the buffer tank is 40-45 ℃, and the air pressure is 0.5-0.6 Mpa;

s2 pumping 25-30 wt.% NaCN aqueous solution from the storage tank to the batching tank, diluting with water to 12-20 wt.% for use; the temperature of the storage tank is 18-20 ℃;

introducing chlorine gas and the diluted NaCN aqueous solution obtained in the step S2 into an S3 reactor, and starting chlorination reaction at 93-95 ℃; the volume ratio of the NaCN aqueous solution to the chlorine is 1 (1-1.02);

circulating reaction liquid in the S4 reactor outside and cooling to keep the temperature in the reactor unchanged;

s5 the chlorinated product cyanogen chloride gas rises in the reactor, and is in countercurrent contact with water from top to bottom through an exchange tower, and unreacted chlorine gas is intercepted back to the reactor; cooling the hydrogen chloride gas from 90-95 ℃ to 30-35 ℃ in the exchange tower;

s6 the cyanogen chloride gas passes through the exchange tower to continuously rise, the temperature of the cyanogen chloride gas is reduced to 10-15 ℃ in a cooler (secondary cooling) at the top of the tower, and condensed water returns to the reactor;

the cyanogen chloride gas after the temperature reduction of S7 is further dewatered by a drier after the entrained water mist is removed by a water mist catcher; the water mist catcher intercepts water, then reaches the top of the reactor and then flows back to the reactor; the flow rate of the hydrogen chloride gas in the water mist catcher is 1000-1200L/h;

when the temperature of the external circulation of the S8 reactor is reduced, a part of the flow is diverted to a resolving kettle, and cyanogen chloride in the liquid phase is gasified and recovered by heating; the resolved liquid phase is the chlorination wastewater which is sent to a reclaimed water workshop for purification and reuse;

s9, in the drying process, calcium sulfate particles are filled in a drying tower, and when cyanogen chloride gas passes through a calcium sulfate particle layer, residual moisture carried by the cyanogen chloride gas is intercepted in the calcium sulfate particles; when the calcium sulfate particles in one drying tower absorb water, the other drying tower is switched to work, and the switched tower is subjected to hot air regeneration to remove adsorbed water for later use;

s10, the dried cyanogen chloride gas enters a polymerization furnace, and is polymerized into cyanuric chloride at high temperature under the action of a catalyst; the polymerization furnace uses heat conducting oil to remove polymerization heat and keep the polymerization temperature stable; the catalyst is a mixture of activated carbon and molybdenum disulfide; the polymerization temperature is 53-55 ℃;

s11 allowing cyanuric chloride to flow out of the polymerization furnace and enter a crystallizer, and meeting with dry cold air to desublimate into a powdery solid product; the temperature of the cold air is 4-6 ℃, and the flow rate is 500-600L/h;

s12, passing unreacted chlorine, unpolymerized cyanogen chloride and uncrystallized cyanuric chloride gas through a trap and a catching bin, and entering a tail gas treatment system along with air; the tail gas tower I spray liquid is 25-30 wt.% of sodium hydroxide aqueous solution, and sodium hypochlorite is generated after chlorine is absorbed; the second tower spraying liquid is water and absorbs residual chlorine; the chlorine-containing water is treated in a sewage treatment plant of a company in a unified way; the qualified tail gas after treatment is discharged at high altitude through an exhaust chimney with the height of 35-40 m;

and after being treated by a sodium hydroxide aqueous solution in a spray tower, the waste gas generated by the regeneration of S13 calcium sulfate hot air is concentrated to a discharge port of a tail gas system and is uniformly discharged.

The preparation method of the heat conduction oil comprises the following steps: and mixing the base oil, the heat-conducting filler, the antioxidant and the passivator, and then homogenizing to obtain the heat-conducting oil.

As a preferred scheme, the preparation method of the heat conduction oil comprises the following steps: mixing 88-95 parts by weight of base oil, 1-4 parts by weight of heat-conducting filler, 1.5-2.8 parts by weight of antioxidant and 0.002-0.007 part by weight of passivator, homogenizing at 13000 and 15000rpm at 25-32 ℃ for 2-5min to obtain the heat-conducting oil.

As a preferred embodiment, the base oil is bis (phenylmethyl) toluene.

The antioxidant is one or a mixture of 3, 3-dithiodipropionic acid di (N-succinimide) ester, 3' -dithiodipropionic acid dimethyl ester and thiopropionic acid furfuryl ester.

The antioxidant system adopted by the invention has good adaptation coordination with other raw materials.

Preferably, the antioxidant is a mixture of 3, 3-dithiodipropionic acid di (N-succinimide) ester, 3' -dithiodipropionic acid dimethyl ester and thiopropionic acid furfuryl ester in a mass ratio of (1-6) to (1-3).

The passivating agent is one or a mixture of two of N, N '-bis (o-hydroxybenzylidene) -1, 2-diaminopropane and N, N' -disalicylic acid water ester-1, 3-diaminopropane.

The passivating agent system adopted by the invention can effectively prevent the phenomenon that the inner wall of the heat conduction pipe is corroded by the induction of the heat conduction oil.

As a preferable scheme, the passivating agent is a mixture of N, N '-bis (o-hydroxybenzylidene) -1, 2-diaminopropane and N, N' -disalicylic acid water ester-1, 3-diaminopropane in a mass ratio of (1-7) to (1-5).

The preparation method of the heat-conducting filler comprises the following steps:

j1 mixing the heat-conducting inorganic substance uniformly by a planetary ball mill through a wet grinding method, and then drying to obtain mixed powder;

j2 mixing the cross-linking agent, long carbon chain ester and methanol and homogenizing to obtain emulsion A;

j3 mixing and stirring the mixed powder, the emulsion A and the synergist, standing, and taking bottom sediment to obtain the heat-conducting filler.

As a preferable scheme, the preparation method of the heat-conducting filler comprises the following steps:

j1 adopts a planetary ball mill, the heat-conducting inorganic matters are uniformly mixed by a wet grinding method, and then the mixture is dried for 2 to 4 hours at the temperature of 140 ℃ and 160 ℃ to obtain mixed powder; in the wet grinding method, the mass ratio of the heat-conducting inorganic substance to water is 1 (1.3-1.7), the ball-material ratio is 10-13) 1, the rotating speed is 400-600rpm, and the wet grinding time is 8-12 h;

j2 mixing the cross-linking agent, long carbon chain ester and methanol at mass ratio of (0.7-1.2) to (3-6) to (10-14) and homogenizing at 12000-14000rpm at 39-46 ℃ for 2-5min to obtain emulsion A;

j3 mixing the mixed powder, the emulsion A and the synergist according to the mass ratio of (8-10): 22-26): 0.6-1.7, stirring for 1-3h at the rotation speed of 600-800rpm at the temperature of 75-85 ℃, standing for 65-75h at the temperature of 10-15 ℃, and taking bottom sediment to obtain the heat-conducting filler.

The heat-conducting inorganic substance is composed of one or more of silicon nitride, silicon boride and boron nitride. Preferably, the heat-conducting inorganic substance consists of silicon nitride, silicon boride and boron nitride in a mass ratio of (10-13): (0.8-1.2): (0.1-0.3).

The silicon nitride has high hardness, abrasion resistance, self-lubricating property, remarkable oxidation resistance at high temperature, strong thermal shock resistance and good heat conductivity; the silicon boride is oxidation resistant, thermal shock resistant and chemical corrosion resistant, and has high strength and stability especially under thermal shock; the boron nitride has the advantages of low friction coefficient, good stability in a high-temperature environment, good thermal shock resistance, high strength, high thermal conductivity, low expansion coefficient and high resistivity. However, if the three heat-conducting inorganic substances are directly added into the heat-conducting base oil as fillers, the particles of the inorganic substances have higher hardness and sharp edges and corners, and scratch and abrasion can still be caused on the inner wall of the heat-conducting pipeline under the conditions of high-speed flow and long-time service, so that the production line has a considerable potential risk in safe operation. Therefore, the invention provides a novel heat-conducting filler and a preparation method thereof, which can obviously reduce the abrasion phenomenon of the heat-conducting inorganic substance on the inner wall of a heat-conducting pipeline while fully utilizing the heat-conducting capability of the heat-conducting inorganic substance; moreover, the heat-conducting filler obtained by the specific method can be cooperated with a conventional heat-conducting oil antioxidant to realize synergism, and the heat stability of the heat-conducting oil is improved by reducing the acid value in a heat-conducting oil system, so that the heat-conducting oil prepared by the method has more reliable high-temperature service performance.

The cross-linking agent is one or a mixture of more of methyl cyclopentenolol propionate, ethyl ethoxymethylene cyanoacetate and tris (hydroxymethyl) aminomethane. Preferably, the cross-linking agent is a mixture of methylcyclopentenol propionate, ethyl ethoxymethylene cyanoacetate and tris (hydroxymethyl) aminomethane in a mass ratio of (1-3) to (1-6) to (1-2).

According to the invention, methyl cyclopentenolol propionate, ethyl ethoxymethylene cyanoacetate and tris (hydroxymethyl) aminomethane are used as cross-linking agents, so that the grafting effect of long-carbon-chain esters, namely lauryl alcohol laurate and glycerol monolaurate, on the surface of the heat-conducting inorganic substance can be enhanced, and the grafting effect is related to the polarizability of the cross-linking agents; the long carbon chain ester can enhance the compatibility between the heat conduction oil system and the heat conduction inorganic particles through long carbon chains, and can prevent the sharp surface of the heat conduction inorganic particles from scratching the inner wall of the heat conduction pipeline.

The long carbon chain ester is one or a mixture of lauryl alcohol laurate and glycerol monolaurate. Preferably, the long-carbon-chain ester is a mixture of lauryl alcohol laurate and glycerol monolaurate in a mass ratio of (1-3) to (1-3).

The synergist is 1, 8-naphthalic anhydride and/or phthalic anhydride. As a preferable scheme, the synergist is a mixture of 1, 8-naphthalic anhydride and phthalic anhydride in a mass ratio of (1-4) to (1-4). As a more preferable scheme, the synergist is a mixture of 1, 8-naphthalic anhydride and phthalic anhydride in a mass ratio of 1: 2.

Oxygen atoms positioned at special sites in 1, 8-naphthalic anhydride and phthalic anhydride can induce the carbon chains of the long carbon chain ester to be spatially intertwined, so that the mechanical elasticity and toughness of the heat-conducting filler can be enhanced, and the service durability and reliability of the heat-conducting filler can be ensured. Moreover, the synergist can be used for synergistically enhancing the oxidation resistance of the heat-conducting oil system of the invention with the 3, 3-dithiodipropionic acid di (N-succinimide) ester in the antioxidant to be used, reducing the acid value and improving the thermal stability of the heat-conducting oil, so as to generate an unexpected synergistic effect, which is supposed to be related to the charge effect between the two anhydrides containing the complex oxygen-containing benzene ring structure and the sulfur-sulfur bond and the nitrogen-containing five-membered heterocyclic ring in the 3, 3-dithiodipropionic acid di (N-succinimide) ester; the nitrogen-oxygen single bond in the 3, 3-dithiodipropionic acid di (N-succinimide) ester can improve the distribution condition of the heat-conducting inorganic particles, thereby further enhancing the heat-conducting capacity of the heat-conducting filler.

The invention has the beneficial effects that:

1. the production process of the cyanuric chloride is composed of a production process flow (high-temperature chlorination method) of one to four sections of a cyanuric chloride workshop and/or a production process flow (low-temperature chlorination method) of five sections of the cyanuric chloride workshop, and the high-quality cyanuric chloride can be safely, environmentally, efficiently and reliably produced.

2. The heat conducting oil is applied to the production process of the cyanuric chloride, so that the reliability of the production process of the cyanuric chloride can be effectively improved, and the high-quality cyanuric chloride can be obtained.

3. Silicon nitride, silicon boride, boron nitride, methyl cyclopentenone alcohol propionate, ethyl ethoxymethylene cyanoacetate, tris (hydroxymethyl) aminomethane, 1, 8-naphthalic anhydride, phthalic anhydride and the like are used as raw materials, so that the heat conduction oil which can enhance the heat conduction capability and the heat stability of the heat conduction oil and reduce the acid value to prolong the service life is obtained, and the heat conduction oil can be applied to the production process of cyanuric chloride to enhance the reliability of the production process, thereby improving the economic benefit.

Detailed Description

The above summary of the present invention is described in further detail below with reference to specific embodiments, but it should not be understood that the scope of the above subject matter of the present invention is limited to the following examples.

Introduction of some raw materials in this application:

bis (phenylmethyl) toluene, available from Tianmen, changchang chemical Co., Ltd, CAS: 26898-17-9.

Di (N-succinimidyl) 3, 3-dithiodipropionate available from my heimairei chemical technologies, CAS: 57757-57-0.

Dimethyl 3,3' -dithiodipropionate, available from my mairei chemical technologies, CAS: 15441-06-2.

Furfuryl thiopropionate, available from my heimaire chemical technologies, CAS: 59020-85-8.

N, N' -bis (ortho-hydroxybenzylidene) -1, 2-diaminopropane, available from my heimaire chemical technologies, inc: 94-91-7.

N, N' -disalicylate-1, 3-diaminopropane, available from shanghai meirel chemical technology ltd, CAS: 120-70-7.

Silicon nitride, available from anseil technologies ltd, CAS: 12033-89-5, purity: 99.9%, cargo number: a61691-500g, specification: α -phase, particle size: 0.5 μm.

Silicon boride, available from anseil technologies ltd, CAS: 12008-29-6, purity: 99.5%, cargo number: a60529-50g, particle size: 1 μm.

Boron nitride, available from anseil technologies ltd, CAS: 10043-11-5, purity: 99.9%, cargo number: e0112725000, particle size: 1 μm.

Methylcyclopentenol propionate, available from wuhananebai pharmaceutical chemicals ltd, CAS: 87-55-8.

Ethyl ethoxymethylene cyanoacetate, available from wuhanxin julian chemical ltd, CAS: 94-05-3.

Tris, available from jiki, shanghai to biochemistry technologies, ltd, CAS: 77-86-1.

Lauryl laurate, available from shanghai hongfan biotechnology limited, CAS: 13945-76-1.

Glycerol monolaurate, available from north of river, leihua biotechnology limited, CAS: 27215-38-9.

1, 8-naphthalic anhydride, available from anseil technologies ltd, CAS: 81-84-5.

Phthalic anhydride, available from anseil technologies ltd, CAS: 85-44-9.

Activated carbon, provided by west asia chemical technology (shandong) ltd, specifications: 120 mesh, CAS: 64365-11-3.

Molybdenum disulfide, provided by anseil technologies ltd, specifications: 150nm, good number: e0112291000, CAS: 1317-33-5.

Example 1

The production process flow (high-temperature chlorination method) of one to four sections of a cyanuric chloride workshop comprises the following steps:

(1) feeding the liquid chlorine from the liquid chlorine storage tank into a gasification device to obtain chlorine; the obtained chlorine gas enters a buffer tank; in the liquid chlorine storage tank, the working liquid level is 2/3, and the working pressure is 0.55 MPa; the temperature in the gasification device is 80 ℃, the air pressure is 0.8MPa, the gasification yield is 450kg/h, and the gasification outlet temperature is 20 ℃; the temperature in the buffer tank is 42 ℃ and the air pressure is 0.55 Mpa;

(2) pumping a 30 wt.% NaCN aqueous solution from a storage tank to a batching tank, diluting with water to a concentration of 15 wt.% for use; the temperature of the storage tank is 20 ℃;

(3) introducing chlorine and the diluted NaCN aqueous solution obtained in the step (2) into the reactor, and starting chlorination reaction at 95 ℃; the volume ratio of the NaCN aqueous solution to the chlorine is 1: 1.01;

(4) the chlorinated product cyanogen chloride gas rises in the reactor, and is cooled to 15 ℃ after passing through a primary cooler and a secondary cooler; in the primary cooler, the temperature of the hydrogen chloride gas is reduced from 90 ℃ to 30 ℃; in the secondary cooler, the hydrogen chloride gas is cooled from 30 ℃ to 15 ℃;

(5) the cyanogen chloride gas after temperature reduction is further dewatered by a drier after entrained water mist is removed by a water mist catcher; the water intercepted by the water mist catcher reaches the top of the reactor and then flows back to the reactor; the flow speed of the hydrogen chloride gas in the water mist catcher is 1100L/h;

(6) waste water from the bottom of the reactor enters a desorption kettle, and cyanogen chloride in the liquid phase is gasified and recovered after being heated to 80 ℃; the resolved liquid phase is the chlorination wastewater which is sent to a reclaimed water workshop for purification and reuse;

(7) in the drying procedure, blocky calcium chloride is filled in the drying tower, and when cyanogen chloride gas passes through a blocky calcium chloride layer, the entrained residual moisture is trapped in the blocky calcium chloride; after absorbing water, the blocky calcium chloride in the drying tower becomes a calcium chloride liquid saturated solution which contains hydrochloric acid and is neutralized and purified by quicklime;

(8) the dried cyanogen chloride gas enters a polymerization furnace and is polymerized into cyanuric chloride at high temperature under the action of a catalyst; the polymerization furnace uses heat conducting oil to remove polymerization heat and keep the polymerization temperature stable; the catalyst is a mixture of activated carbon and molybdenum disulfide; the polymerization temperature is 380 ℃;

(9) the gaseous cyanuric chloride is discharged from a polymerization furnace and enters a crystallizer to meet with dry cold air, and the gaseous cyanuric chloride is desublimated into a powdery solid product; the temperature of the cold air is 5 ℃, and the flow rate is 600L/h;

(10) unreacted chlorine gas, unpolymerized cyanogen chloride and uncrystallized cyanuric chloride gas pass through a trap and a catching bin and enter a tail gas treatment system along with air; absorbing chlorine gas by using a sodium hydroxide aqueous solution with the concentration of 30 wt.% of a spraying liquid in the tail gas tower I to generate sodium hypochlorite; the second tower spraying liquid is water and absorbs residual chlorine;

(11) the qualified tail gas after treatment is discharged in high altitude through an exhaust chimney with the height of 40 m;

(12) ventilating and exhausting air in the workshop, treating the air in the environment-friendly tower by using a sodium hydroxide aqueous solution with the concentration of 30 wt.%, concentrating the air to a discharge port of a tail gas system, uniformly discharging the air, spraying the sodium hydroxide aqueous solution by the environment-friendly tower, and sending the sodium hydroxide aqueous solution to a tail gas spraying tower for continuous use.

Example 2

The production process flow (low-temperature chlorination method) of the five sections of the cyanuric chloride workshop comprises the following steps:

s1, feeding the liquid chlorine from the liquid chlorine storage tank into a gasification device to obtain chlorine; the obtained chlorine gas enters a buffer tank; in the liquid chlorine storage tank, the working liquid level is 2/3, and the working pressure is 0.55 MPa; the temperature in the gasification device is 80 ℃, the air pressure is 0.8MPa, the gasification yield is 450kg/h, and the gasification outlet temperature is 20 ℃; the temperature in the buffer tank is 42 ℃ and the air pressure is 0.55 Mpa;

s2 pumping 30 wt.% NaCN aqueous solution from a storage tank to a batching tank, diluting with water to a concentration of 15 wt.% for use; the temperature of the storage tank is 20 ℃;

introducing chlorine gas and the diluted NaCN aqueous solution obtained in the step S2 into an S3 reactor, and starting chlorination reaction at 95 ℃; the volume ratio of the NaCN aqueous solution to the chlorine is 1: 1.01;

circulating reaction liquid in the S4 reactor outside and cooling to keep the temperature in the reactor unchanged;

s5 the chlorinated product cyanogen chloride gas rises in the reactor, and is in countercurrent contact with water from top to bottom through an exchange tower, and unreacted chlorine gas is intercepted back to the reactor; cooling the hydrogen chloride gas from 90 ℃ to 30 ℃ in the exchange column;

s6, the cyanogen chloride gas passes through the exchange tower to continuously rise, the temperature of the cyanogen chloride gas is reduced to 15 ℃ in a cooler (secondary cooling) at the top of the tower, and condensed water returns to the reactor;

the cyanogen chloride gas after the temperature reduction of S7 is further dewatered by a drier after the entrained water mist is removed by a water mist catcher; the water mist catcher intercepts water, then reaches the top of the reactor and then flows back to the reactor; the flow speed of the hydrogen chloride gas in the water mist catcher is 1100L/h;

when the temperature of the external circulation of the S8 reactor is reduced, a part of the flow is diverted to a resolving kettle, and cyanogen chloride in the liquid phase is gasified and recovered by heating; the resolved liquid phase is the chlorination wastewater which is sent to a reclaimed water workshop for purification and reuse;

s9, in the drying process, calcium sulfate particles are filled in a drying tower, and when cyanogen chloride gas passes through a calcium sulfate particle layer, residual moisture carried by the cyanogen chloride gas is intercepted in the calcium sulfate particles; when the calcium sulfate particles in one drying tower absorb water, the other drying tower is switched to work, and the switched tower is subjected to hot air regeneration to remove adsorbed water for later use;

s10, the dried cyanogen chloride gas enters a polymerization furnace, and is polymerized into cyanuric chloride at high temperature under the action of a catalyst; the polymerization furnace uses heat conducting oil to remove polymerization heat and keep the polymerization temperature stable; the catalyst is a mixture of activated carbon and molybdenum disulfide; the polymerization temperature is 55 ℃;

s11 allowing cyanuric chloride to flow out of the polymerization furnace and enter a crystallizer, and meeting with dry cold air to desublimate into a powdery solid product; the temperature of the cold air is 5 ℃, and the flow rate is 600L/h;

s12, passing unreacted chlorine, unpolymerized cyanogen chloride and uncrystallized cyanuric chloride gas through a trap and a catching bin, and entering a tail gas treatment system along with air; the tail gas tower I spray liquid is sodium hydroxide aqueous solution with the concentration of 30 wt.%, and sodium hypochlorite is generated after chlorine is absorbed; the second tower spraying liquid is water and absorbs residual chlorine; the qualified tail gas after treatment is discharged in high altitude through an exhaust chimney with the height of 40 m;

and after being treated by a sodium hydroxide aqueous solution in a spray tower, the waste gas generated by the regeneration of S13 calcium sulfate hot air is concentrated to a discharge port of a tail gas system and is uniformly discharged.

Example 3

The production process flow (high-temperature chlorination method) of one to four sections of a cyanuric chloride workshop comprises the following steps:

(1) feeding the liquid chlorine from the liquid chlorine storage tank into a gasification device to obtain chlorine; the obtained chlorine gas enters a buffer tank; in the liquid chlorine storage tank, the working liquid level is 2/3, and the working pressure is 0.55 MPa; the temperature in the gasification device is 80 ℃, the air pressure is 0.8MPa, the gasification yield is 450kg/h, and the gasification outlet temperature is 20 ℃; the temperature in the buffer tank is 42 ℃ and the air pressure is 0.55 Mpa;

(2) pumping a 30 wt.% NaCN aqueous solution from a storage tank to a batching tank, diluting with water to a concentration of 15 wt.% for use; the temperature of the storage tank is 20 ℃;

(3) introducing chlorine and the diluted NaCN aqueous solution obtained in the step (2) into the reactor, and starting chlorination reaction at 95 ℃; the volume ratio of the NaCN aqueous solution to the chlorine is 1: 1.01;

(4) the chlorinated product cyanogen chloride gas rises in the reactor, and is cooled to 15 ℃ after passing through a primary cooler and a secondary cooler; in the primary cooler, the temperature of the hydrogen chloride gas is reduced from 90 ℃ to 30 ℃; in the secondary cooler, the hydrogen chloride gas is cooled from 30 ℃ to 15 ℃;

(5) the cyanogen chloride gas after temperature reduction is further dewatered by a drier after entrained water mist is removed by a water mist catcher; the water mist catcher intercepts water, then reaches the top of the reactor and then flows back to the reactor; the flow speed of the hydrogen chloride gas in the water mist catcher is 1100L/h;

(6) waste water from the bottom of the reactor enters a desorption kettle, and cyanogen chloride in the liquid phase is gasified and recovered after being heated to 80 ℃; the resolved liquid phase is the chlorination wastewater which is sent to a reclaimed water workshop for purification and reuse;

(7) in the drying procedure, blocky calcium chloride is filled in the drying tower, and when cyanogen chloride gas passes through a blocky calcium chloride layer, the entrained residual moisture is trapped in the blocky calcium chloride; after absorbing water, the blocky calcium chloride in the drying tower becomes a calcium chloride liquid saturated solution which contains hydrochloric acid and is neutralized and purified by quicklime;

(8) the dried cyanogen chloride gas enters a polymerization furnace and is polymerized into cyanuric chloride at high temperature under the action of a catalyst; the polymerization furnace uses heat conducting oil to remove polymerization heat and keep the polymerization temperature stable; the catalyst is a mixture of activated carbon and molybdenum disulfide in a mass ratio of 17: 1; the polymerization temperature is 380 ℃;

(9) the gaseous cyanuric chloride is discharged from a polymerization furnace and enters a crystallizer to meet with dry cold air, and the gaseous cyanuric chloride is desublimated into a powdery solid product; the temperature of the cold air is 5 ℃, and the flow rate is 600L/h;

(10) unreacted chlorine gas, unpolymerized cyanogen chloride and uncrystallized cyanuric chloride gas pass through a trap and a catching bin and enter a tail gas treatment system along with air; absorbing chlorine gas by using a sodium hydroxide aqueous solution with the concentration of 30 wt.% of a spraying liquid in the tail gas tower I to generate sodium hypochlorite; the second tower spraying liquid is water and absorbs residual chlorine;

(11) the qualified tail gas after treatment is discharged in high altitude through an exhaust chimney with the height of 40 m;

(12) ventilating and exhausting air in the workshop, treating the air in the environment-friendly tower by using a sodium hydroxide aqueous solution with the concentration of 30 wt.%, concentrating the air to a discharge port of a tail gas system, uniformly discharging the air, spraying the sodium hydroxide aqueous solution by the environment-friendly tower, and sending the sodium hydroxide aqueous solution to a tail gas spraying tower for continuous use.

The preparation method of the heat conduction oil comprises the following steps: 92 parts by weight of base oil, 3 parts by weight of heat-conducting filler, 2.3 parts by weight of antioxidant and 0.006 part by weight of passivating agent are mixed and homogenized at the rotating speed of 15000rpm at 30 ℃ for 3min to obtain the heat-conducting oil.

The base oil is bis (phenylmethyl) toluene.

The antioxidant is a mixture of 3, 3-dithiodipropionic acid di (N-succinimide) ester, 3' -dithiodipropionic acid dimethyl ester and thiopropionic acid furfuryl ester in a mass ratio of 2:1: 1.

The passivating agent is a mixture of N, N '-bis (o-hydroxybenzylidene) -1, 2-diaminopropane and N, N' -disalicylic acid water ester-1, 3-diaminopropane in a mass ratio of 5: 2.

The preparation method of the heat-conducting filler comprises the following steps:

j1 mixing the heat-conducting inorganic substance uniformly by a planetary ball mill through a wet grinding method, and then drying for 3h at 150 ℃ to obtain mixed powder; in the wet grinding method, the mass ratio of the heat-conducting inorganic substance to water is 1:1.6, the ball-material ratio is 12:1, the rotating speed is 600rpm, and the wet grinding time is 10 hours; the heat-conducting inorganic substance is composed of silicon nitride, silicon boride and boron nitride according to the mass ratio of 12:1: 0.3;

j2 mixing the cross-linking agent, long carbon chain ester and methanol at a mass ratio of 1:4:12, and homogenizing at 40 deg.C at 14000rpm for 3min to obtain emulsion A; the cross-linking agent is a mixture of methyl cyclopentenolol propionate, ethyl ethoxymethylene cyanoacetate and tris (hydroxymethyl) aminomethane in a mass ratio of 1:4: 2; the long carbon chain ester is a mixture of lauryl alcohol laurate and glycerol monolaurate in a mass ratio of 2: 1;

j3, mixing the mixed powder, the emulsion A and the synergist in a mass ratio of 9:23:1, stirring at 80 ℃ for 2 hours at a rotating speed of 700rpm, standing at 12 ℃ for 70 hours, and taking bottom sediment to obtain the heat-conducting filler; the synergist is a mixture of 1, 8-naphthalic anhydride and phthalic anhydride in a mass ratio of 1: 2.

Example 4

Essentially the same as example 3, except that: the synergist is 1, 8-naphthalic anhydride.

Example 5

Essentially the same as example 3, except that: the synergist is phthalic anhydride.

Example 6

Essentially the same as example 3, except that: the preparation method of the heat conduction oil comprises the following steps: 92 parts by weight of base oil, 3 parts by weight of heat-conducting filler, 2.3 parts by weight of antioxidant and 0.006 part by weight of passivating agent are mixed and homogenized at the rotating speed of 15000rpm at 30 ℃ for 3min to obtain the heat-conducting oil.

The base oil is bis (phenylmethyl) toluene.

The antioxidant is a mixture of 3, 3-dithiodipropionic acid di (N-succinimide) ester, 3' -dithiodipropionic acid dimethyl ester and thiopropionic acid furfuryl ester in a mass ratio of 2:1: 1.

The passivating agent is a mixture of N, N '-bis (o-hydroxybenzylidene) -1, 2-diaminopropane and N, N' -disalicylic acid water ester-1, 3-diaminopropane in a mass ratio of 5: 2.

The preparation method of the heat-conducting filler comprises the following steps:

j1 mixing the heat-conducting inorganic substance uniformly by a planetary ball mill through a wet grinding method, and then drying for 3h at 150 ℃ to obtain mixed powder; in the wet grinding method, the mass ratio of the heat-conducting inorganic substance to water is 1:1.6, the ball-material ratio is 12:1, the rotating speed is 600rpm, and the wet grinding time is 10 hours; the heat-conducting inorganic substance is composed of silicon nitride, silicon boride and boron nitride according to the mass ratio of 12:1: 0.3;

j2 mixing the cross-linking agent, long carbon chain ester and methanol at a mass ratio of 1:4:12, and homogenizing at 40 deg.C at 14000rpm for 3min to obtain emulsion A; the cross-linking agent is a mixture of methyl cyclopentenolol propionate, ethyl ethoxymethylene cyanoacetate and tris (hydroxymethyl) aminomethane in a mass ratio of 1:4: 2; the long carbon chain ester is a mixture of lauryl alcohol laurate and glycerol monolaurate in a mass ratio of 2: 1;

j3 mixing the mixed powder and the emulsion A according to the mass ratio of 9:23, stirring at 80 ℃ for 2h at the rotating speed of 700rpm, standing at 12 ℃ for 70h, and taking bottom sediment to obtain the heat-conducting filler.

Example 7

Essentially the same as example 3, except that:

the preparation method of the heat conduction oil comprises the following steps: mixing 92 parts by weight of base oil, 3 parts by weight of graphene, 2.3 parts by weight of antioxidant and 0.006 part by weight of passivating agent, homogenizing at the temperature of 30 ℃ and the rotating speed of 15000rpm for 3min to obtain the heat conduction oil.

The base oil is bis (phenylmethyl) toluene.

The antioxidant is a mixture of 3, 3-dithiodipropionic acid di (N-succinimide) ester, 3' -dithiodipropionic acid dimethyl ester and thiopropionic acid furfuryl ester in a mass ratio of 2:1: 1.

The passivating agent is a mixture of N, N '-bis (o-hydroxybenzylidene) -1, 2-diaminopropane and N, N' -disalicylic acid water ester-1, 3-diaminopropane in a mass ratio of 5: 2.

Example 8

Essentially the same as example 3, except that:

the preparation method of the heat conduction oil comprises the following steps: 92 parts by weight of base oil, 3 parts by weight of heat-conducting filler, 2.3 parts by weight of antioxidant and 0.006 part by weight of passivating agent are mixed and homogenized at the rotating speed of 15000rpm at 30 ℃ for 3min to obtain the heat-conducting oil.

The base oil is bis (phenylmethyl) toluene.

The antioxidant is a mixture of dimethyl 3,3' -dithiodipropionate and furfuryl thiopropionate in a mass ratio of 1:1.

The passivating agent is a mixture of N, N '-bis (o-hydroxybenzylidene) -1, 2-diaminopropane and N, N' -disalicylic acid water ester-1, 3-diaminopropane in a mass ratio of 5: 2.

The preparation method of the heat-conducting filler comprises the following steps:

j1 mixing the heat-conducting inorganic substance uniformly by a planetary ball mill through a wet grinding method, and then drying for 3h at 150 ℃ to obtain mixed powder; in the wet grinding method, the mass ratio of the heat-conducting inorganic substance to water is 1:1.6, the ball-material ratio is 12:1, the rotating speed is 600rpm, and the wet grinding time is 10 hours; the heat-conducting inorganic substance is composed of silicon nitride, silicon boride and boron nitride according to the mass ratio of 12:1: 0.3;

j2 mixing the cross-linking agent, long carbon chain ester and methanol at a mass ratio of 1:4:12, and homogenizing at 40 deg.C at 14000rpm for 3min to obtain emulsion A; the cross-linking agent is a mixture of methyl cyclopentenolol propionate, ethyl ethoxymethylene cyanoacetate and tris (hydroxymethyl) aminomethane in a mass ratio of 1:4: 2; the long carbon chain ester is a mixture of lauryl alcohol laurate and glycerol monolaurate in a mass ratio of 2: 1;

j3, mixing the mixed powder, the emulsion A and the synergist in a mass ratio of 9:23:1, stirring at 80 ℃ for 2 hours at a rotating speed of 700rpm, standing at 12 ℃ for 70 hours, and taking bottom sediment to obtain the heat-conducting filler; the synergist is a mixture of 1, 8-naphthalic anhydride and phthalic anhydride in a mass ratio of 1: 2.

Example 9

Essentially the same as example 3, except that: the catalyst is activated carbon.

Test example 1

Testing the heat conductivity coefficient of the heat conducting oil: the thermal conductivity of the thermal oil obtained by the embodiments of the present invention was determined according to GB/T22588-. For each case, 5 samples were tested and the results averaged. The test temperature was 430 ℃.

The test results are shown in table 1.

TABLE 1 thermal conductivity of Heat transfer oils

Test example 2

Testing the acid value of the heat transfer oil: the acid value of the heat transfer oil obtained by each example of the present invention was measured according to method A in GB/T7304-. A calomel electrode is used as a reference electrode; an automatic potentiometric titration method is adopted. For each case, 5 samples were tested and the results averaged.

The test results are shown in table 2.

TABLE 2 acid number of Heat transfer oils

Test example 3

Testing the thermal stability of the heat-conducting oil: the thermal stability of the heat transfer oil obtained from the examples of the present invention was determined according to GB/T23800-2009 thermal stability assay for organic Heat Carrier. The test temperature was 430 ℃ and the test duration was 720 h. For each case, 5 samples were tested and the results averaged.

The test results are shown in table 3.

TABLE 3 thermal stability of Heat transfer oils

Test example 4

Testing the quality of cyanuric chloride: the quality of cyanuric chloride produced in examples 3 and 9 of the present invention was determined according to GB/T25814-2010 "cyanuric chloride".

The test results are shown in table 4.

TABLE 4 quality of cyanuric chloride

The silicon nitride has high hardness, abrasion resistance, self-lubricating property, remarkable oxidation resistance at high temperature, strong thermal shock resistance and good heat conductivity; the silicon boride is oxidation resistant, thermal shock resistant and chemical corrosion resistant, and has high strength and stability especially under thermal shock; the boron nitride has the advantages of low friction coefficient, good stability in a high-temperature environment, good thermal shock resistance, high strength, high thermal conductivity, low expansion coefficient and high resistivity. However, if the three heat-conducting inorganic substances are directly added into the heat-conducting base oil as fillers, the particles of the inorganic substances have higher hardness and sharp edges and corners, and scratch and abrasion can still be caused on the inner wall of the heat-conducting pipeline under the conditions of high-speed flow and long-time service, so that the production line has a considerable potential risk in safe operation. Therefore, the invention provides a novel heat-conducting filler and a preparation method thereof, which can obviously reduce the abrasion phenomenon of the heat-conducting inorganic substance on the inner wall of a heat-conducting pipeline while fully utilizing the heat-conducting capability of the heat-conducting inorganic substance; moreover, the heat-conducting filler obtained by the specific method can be cooperated with a conventional heat-conducting oil antioxidant to realize synergism, and the heat stability of the heat-conducting oil is improved by reducing the acid value in a heat-conducting oil system, so that the heat-conducting oil prepared by the method has more reliable high-temperature service performance.

According to the invention, methyl cyclopentenolol propionate, ethyl ethoxymethylene cyanoacetate and tris (hydroxymethyl) aminomethane are used as cross-linking agents, so that the grafting effect of long-carbon-chain esters, namely lauryl alcohol laurate and glycerol monolaurate, on the surface of the heat-conducting inorganic substance can be enhanced, and the grafting effect is related to the polarizability of the cross-linking agents; the long carbon chain ester can enhance the compatibility between the heat conduction oil system and the heat conduction inorganic particles through long carbon chains, and can prevent the sharp surface of the heat conduction inorganic particles from scratching the inner wall of the heat conduction pipeline.

Oxygen atoms positioned at special sites in 1, 8-naphthalic anhydride and phthalic anhydride can induce the carbon chains of the long carbon chain ester to be spatially intertwined, so that the mechanical elasticity and toughness of the heat-conducting filler can be enhanced, and the service durability and reliability of the heat-conducting filler can be ensured. Moreover, the synergist can be used for synergistically enhancing the oxidation resistance of the heat-conducting oil system of the invention with the 3, 3-dithiodipropionic acid di (N-succinimide) ester in the antioxidant to be used, reducing the acid value and improving the thermal stability of the heat-conducting oil, so as to generate an unexpected synergistic effect, which is supposed to be related to the charge effect between the two anhydrides containing the complex oxygen-containing benzene ring structure and the sulfur-sulfur bond and the nitrogen-containing five-membered heterocyclic ring in the 3, 3-dithiodipropionic acid di (N-succinimide) ester; the nitrogen-oxygen single bond in the 3, 3-dithiodipropionic acid di (N-succinimide) ester can improve the distribution condition of the heat-conducting inorganic particles, thereby further enhancing the heat-conducting capacity of the heat-conducting filler.

In the production process of the cyanuric chloride, the molybdenum disulfide and the activated carbon are mixed to be used as the catalyst, so that the cyanuric chloride with higher quality is obtained.