JPH01502262A - Antimony thioantimonate lubricating oil additive and its production - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Thioantimony Antimony moisturizing oil, Sai and L211 1 bean skin 1 yen Antimony thioantimonate Sb (SbS,) is useful as a lubricating oil additive. be. This compound shows that each of the two antimony atoms is probably in a different valence state. It is actually a "complex" compound in that it exists in the +3 and +4 states.

Antimony thioantimonate Sb (SbS,) is oxidized in an aqueous medium. Antimony (dissolved in concentrated potassium hydroxide solution) is dissolved in sodium thioammonate ( NasSbS4) and neutralizing the resulting solution with acid. One example that has been created is that of J.P. King and Yanis Asmerom. 11vestigation of Extreme-Pressure a nd Antiwear Properties of Anti-oney “Thioantimonate” [ASLE Transaction, vol. 24.4.497-504 (1981)] and Mr. Soren's US special edition. See Patent No. 3,965,016 (issued June 22, 1976). The entire reaction can be written as:

The above reaction has severe limitations, namely: (1) free sulfur (6%) associated with the final product; It is accompanied by the generation of hydrogen sulfide during coprecipitation and (2) neutralization. According to subsequent research For example, it was shown that the following side reactions occur simultaneously during the neutralization process.

2Na, +5bS4+6H"-→5bSbS4+3H2S+S+6Na" (2 ) Excess of free sulfur in lubricating oil additives (such as 5bsbs, and others) (approximately 1% or more) is extremely Undesirable free sulfur is removed from the final product and costs are spent collecting H,S. Improved and economical manufacturing for manufacturing 5bsbs due to the cost of use Law is highly desirable.

The present invention provides a simple processing procedure for producing 5bsbs with low sulfur content. It includes an improved reaction route including This new method reduces free sulfur by approximately 1% 5bsbs, containing at more acceptable levels of Wear. Furthermore, the formation of His and hydrolysis or other decomposition products is virtually eliminated. . Moreover, the method can be easily controlled and operated as a continuous method. .

Furthermore, the method is made -1 more economical. This is because it is stabilized with halides. The antimony trihalide reactant was prepared by treating 5biOs with concentrated HCl and NaCl. The conventional antimony trihalide can be prepared by reaction in the form of an aqueous solution without the severe hydrolysis and decomposition problems normally associated with This is because it can be preferably used in the form of Na5C1- as a reactive substance.

The present invention continuously feeds the two reactants into the reactor and then 5 bsbs, To produce antimony thioantimonate 5bsbs, by extracting It includes a novel method for The reaction products are then centrifuged as part of a continuous process. Separated, washed and dried. Water Soluble Halide Stabilized Trihalogen By using an antimony chloride complex as one of the starting materials, the method is Economics are significantly improved and the overall processing operation is improved with increased yield and decomposition and/or ) are greatly improved, including lower levels of undesirable products of side reactions.

Menzudate 11 Broadly speaking, the method of the present invention involves the use of alkali metal thioantimonates and halide mixing an aqueous solution of stabilized antimony trihalide to form a reaction mixture; and maintaining the reaction mixture at a pH below 7 to have a low free sulfur impurity level; 5bsbs, which has low free sulfur impurity levels from forming the product. 5bsbs, a method for producing a compound.

Preferably, the alkali metal thioantimonate is sodium thioantimonate. , the trihalide is antimony trichloride, and the pH in the reaction mixture is 7. is maintained below.

The alkali metal thioantimonate and trihalide solutions are rapidly mixed and then The trihalide is present in molar excess to provide low free sulfur impurity levels. It is preferable to do so.

When carrying out the process as a batch process, the alkali metal thioantimonate Add to halide solution with mixing. As a fast-acting method, thioanti The alkali metal monate and ternary compound solutions are continuously metered into the mixing zone where they are From 5 bsbs onwards, the product is discharged as a slurry.

Preferred reaction temperatures are below about 3Q''C.

Halide-stabilized antimony trihalide is a mixture of 5b20s and concentrated HX. to form an aqueous solution of halide-stabilized antimony trihalide. It is formed by applying specific reaction conditions. The trihalide complex is HSbX , (where X is a halogen, preferably C1), Add excess NaCl and some additional Sbz to the solution as shown in the examples. It is preferred to add Os, HCl is preferably added in slight excess ( The stoichiometric amount is 6 moles of HCI per mole of SbzOs).

Also, trihalides can be produced in the same way as sb gold metal instead of SbzOs. However, in this case it is preferable to also use an oxidizing agent such as H-Oa.

5 bbsbs, the product was separated from the reaction mixture to determine the chloride content of the mosiso product. Washed to reduce to below 300 ppm.

A continuous method of carrying out the invention is: (a) Alkali metal thioantimonate and halide stabilized triherogonide Reactive mixing by metering a separate stream of an aqueous solution of timone into the mixing zone at a controlled rate form things, (b) maintaining a pH below 7 in the reaction mixture, and then (c) low free sulfur consisting of withdrawing 5 bsbs of product from the mixing zone; 5bsbs with impurity level.

method of manufacturing the product; It is stipulated that

The most preferred pH of the reaction mixture is below 5. In continuous methods, the pH is , best maintained by adjusting the ratio of the dispensing rates of the separate streams. Also preferred is the use of Na5bC1, complex.

The 5bsbs4 product has a chloride content of 300 p based on the weight of the product. Washed to reduce below pm.

In continuous processes, preferably the withdrawn product and the residual reaction mixture are continuously Transfer to receiver under mixing.

°The product of the invention can be used as the 5bsbs, product or alternatively of the above process. bsbs, and halide-stabilized antimony trihalide (preferably Sb C1g at a concentration of less than 300 ppm).

p-delightful ho The nature of The raw material (Na5Sb 5bC1s complex). 2 The proportionality of the two raw materials is first established by titration, and the metering pump is accordingly The desired p)I of the reaction mixture for which p is set is 3, and this Adjusted by varying the rate of dispensing.

5 bbsbs, the slurry was transferred from the holding tank to a 24 in. center slug (cent. pump to the other feed tank located directly above the centrifuge. will be removed. The material is gravity fed into a centrifuge until a suitable cake is formed . This cake is cut and brought to an acceptable limit of chloride level, i.e. 3. Keto with a stirrer by belt feeder to reduce to less than 0.00 ppm It is then sent to the bathroom for cleaning.

The present invention provides (a) inexpensive and stable starting materials (halide-stabilized antimony trihalide complexes); (b) both free sulfur and hydrogen sulfide by-products; (C) continuous treatment process; (d) readily disposed of; (e) higher yields than existing methods; supply

The present invention is based on the reaction of 5btOs with concentrated hydrochloric acid and NaCl (excess). and the use of an aqueous solution of a halide-stabilized antimony trichloride complex. this The complex is stable in a low pH range and has a good shelf life. complex The ionic formula appears to be (SbC14)- and the complex is Na5bC14. It is preferable to

The most critical features of the invention are: (i) maintaining the pH of the reaction medium below 7; and (N) halide stabilized antimony thioantimonate. It seems that.

Rapid mixing of the reactants ensures that the pH is always below 7 within all parts of the mixing zone. (HSbCl, or Na5bC14 solution) is highly acidic, whereas Na5SbS4 is highly basic and typical has a pH of about 11).

Additionally, a molar excess typically 2 to 20% (preferably 2 to 10%) Examples 1 to 10 (shown in Table 1) in which it is preferable to use chloride complexes are shown in Table 1. Species reaction parameters: overall yield, free sulfur content, hydrogen sulfide release and chloride content. The reaction order and starting materials in the present invention are examples of how the and the generated by-products are shown in the next step.

I, 3Na*S'98*0+2S+Sb*Ss-→2NasSbSn”27 HtOI1. Sb! O3+6HC1◆2C1−−−→2SbC1,−◆3H8O m, Na5SbSa-+5bct4--→5bSbS4+3Na""+4 The results of CI-Examples 1-9 are shown in Table 1.

The production of Na5SbS4 (reactor) is described in U.S. Patent No. 3.965.016. It is.

The production of HSbCl (reaction II) consists of white Sb*Os and 37-39%) TCI heating the mixture with stirring to 70-75°C to form a clear solution. Therefore, the final product including the reaction temperature, addition time, stirring speed, etc. The details of the production (reaction ■) of 5bsbs are shown in Table 1.0 reaction pressure is the reaction ■ can provide the chloride ions needed (recycled) in the final student The composition is washed with distilled water or 1% NaHCOs or both.

The mole % value (H2s/5bSbS,), which is a measure of free Has, is , S was obtained by precipitation. This is 5bsbs, the emission from the reaction 0 generated Has by passing the gas through an aqueous solution of Pb (OAC) is precipitated as PbS, which is collected, dried and weighed* From the weight of P e S and the measured yield of 5bsbs4, Ha for 5bsbs The mol% of s is calculated (for example, H*S moles ÷ 5bSbS, -[-/l , number x 100).

Higejou Example 11 illustrates continuous process conditions for large scale production of 5 bbsbs. It is.

Oan Mon Natoum'. , Engineering) Typical for producing Na5bC1 In a typical reaction, 210 gallons of “KYNAR” (Pennwalt Corp. Product name for polyvinylidene fluoride film) reaction with lining stirrer First, 140 gallons of boiling water (180'F) was added to the reactor using a Sodium sulfide (Nag s・3820) of b, antimony sulfide of 1371b ( This mixture, charged with sulfur powder of SbzSs) and 251b, was heated to 200°F. Heat and hold for 4 hours at zero temperature), add 6 gallons of cold water and add Na5SbS. Prevent the crystallization of 4 and boil the solution with brine for 32 L: Cool and then filter and store the entire contents through a 5 micron bag filter. I put it in a weak condition.

In other instances, the material was filtered through a carbon filter.

In yet another example, the solution is allowed to stand and is decantated into a clear) Ta.

Halogen substances - antimony solution In a typical reaction to produce a halide-stabilized 5bC1s solution, a stirrer Hastelloy “C° Kettle Kai” was used. Two 34 gallon (3241b) Add Baume hydrochloric acid to the reactor, then add 5ltOs of antimony oxide 681b. Ta. This was mixed until it became a solution.Next, sodium chloride of 711b was added. Then, with continuous stirring, 681b of antimony oxide was gradually added to C; The solution was then filtered through a carbon filter and placed in a storage container. Ta.

The equilibrium reaction equation for this reaction is thought to be as follows.

5bzOs”68C++2NaC1-→2NaSbC1-”aHJ+excess Na C1 Thus, 6 moles of HCI are required per mole of Sb*Os and Na C1 is present in excess.

5biOs is preferably 5b20. Added in two parts to increase solubilization of If NaC] addition is preceded, one-step addition of 5bzOs is required. It can be carried out in

Toned blue of sodium rum melt Add 110 gallons of water and then 2601b of sodium chloride to an agitated reactor. , and mixed until the salt was dissolved.

Thioantimony - Antimony B Three pre-prepared solutions (NasSbS, 5bC1s, NaC1) are metered out. Reactor (Kennick Miki) with Randolph tube pump for ). The product is transferred from a Kenic mixer with a stirrer. Pump into receiver. In the laboratory, Na5SbS4 and 5bC1s complex solutions are The sample is first reacted to obtain the appropriate volume ratio to provide the desired pH of 3±2.

This information provides initial metering for pumping the 5bC1s and Na5SbS solutions. Used to set feed rate. 5bsbs, centrifuge the product slurry and washed to remove MCI and sodium chloride.The product was then dried. Then the powder base was removed.

Sodium chloride solution in 5bsbs with stirrer, receiver (raw from Kenic mixer) (received the product) until it covered its mixer blades. halide Stabilized 5bC1s and Na5SbS, solution pumps were started to start the process. . Monitor the pH of the product effluent to the receiver. If the pH is outside the range of approximately 2-4, The metering pump was adjusted when

international search report

Claims (44)

[Claims] 1. Alkali metal thioantimonate and halide stabilized trihalide anti to form a reaction mixture, and the reaction mixture is lower than 7. Maintain pH to produce SbSbS4 product with low free sulfur impurity levels. Production of SbSbS4 compounds with low free sulfur impurity levels consisting of Law. 2. The alkali metal thioantimonate is sodium thioantimonate, and The method according to claim 1, wherein the trihalide is antimony trichloride. 3. 2. The method of claim 1, wherein the pH is lower than 4. 4. Alkali metal thioantimonate and trihalide solutions are rapidly mixed A method according to claim 1, 2 or 3. 5. The trihalide is present in molar excess to provide low free sulfur impurity levels. 4. The method of claim 4. 6. The process is a batch process and the alkali metal thioantimonate is a trihalogen 5. The method of claim 4, wherein the method is added to the genide solution with mixing. 7. The process is a continuous process and the alkali metal antimonate and trihalogen The compound solution is continuously metered into the mixing zone from which the SbSbS4 product is 5. The method according to claim 4, wherein the slurry is discharged as a slurry. 8. 5. The method of claim 4, wherein the reaction mixture is maintained at a temperature below about 30°C. Method. 9. Halide-stabilized antimony trihalide stabilizes Sb203 and concentrated HCl. Producing an aqueous solution of halide-stabilized antimony trihalide for mixtures containing Claim 4, which is formed by applying reaction conditions to Method. 10. Claims the mixture contains excess NaCl to produce NaSbCl4 The method described in Scope Item 9. 11. 10. The method of claim 9, wherein the mixture includes antimony metal. 12. Claims the mixture contains excess NaCl to produce NaSbCl4 The method according to scope item 11. 13. Halide-stabilized antimony trihalides contain antimony metal and concentrated H Aqueous solutions of halide-stabilized antimony trihalides for mixtures containing Cl Claim 4 formed by applying reaction conditions to produce Method described. 14. 14. The method of claim 13, wherein the mixture comprises NaCl. 15. Claim 1, wherein the trihalide is a complex containing (SbCl4)- ion. The method according to item 1, 2 or 5. 16. Trihalide complexes include HSbCl4, NaSbCl4, HSbCl4 water selected from the group consisting essentially of hydrate, NaSbCl4hydrate and mixtures thereof. 16. The method according to claim 15. 17. The alkali metal thioantimonate and trihalide solutions are rapidly mixed. 16. The method according to claim 15. 18. trihalide in molar excess to provide low free sulfur indurate levels. 16. The method of claim 15 residing in 19. The process is a batch process and the alkali metal thioantimonate is 16. The method of claim 15, wherein the method is added to the halide solution with mixing. 20. The process is a continuous process and alkali metal thioantimonates and A logeside solution is continuously metered into the mixing zone, from which SbSbS4 is produced. 16. The method of claim 15, wherein the material is discharged as a slurry. 21. Claim 15, wherein the reaction mixture is maintained at a temperature below about 30°C. How to put it on. 22. The SbSbS4 product is separated from the reaction mixture and then the chloride content of the product is Claim 4: Washed to reduce the amount below 300 ppm. the method of. 23. SbSbS4 compound of the method according to claim 4. 24. (a) Alkali metal and halide stabilized trihalogen thioantimonates A separate stream of an aqueous solution of antimony chloride is metered into the mixing zone at a controlled rate to react. forming a reaction mixture; (b) maintaining a pH below 7 in the reaction mixture and then (c) low free sulfur comprising pumping out SbSbS4 products from the mixing zone; A method for producing SbSbS4 compounds with impurity levels. 25. The alkali metal thioantimonate is sodium thioantimonate; 25. The method according to claim 24, wherein the trihalide is antimony trichloride. 26. 26. The method of claim 25, wherein the pH is lower than 4. 27. The alkali metal thioantimonate and trihalide solutions are rapidly mixed. 27. The method according to claim 24, 25 or 26. 28. The pH of the reaction mixture can be adjusted by adjusting the ratio of the metering rates of the separate streams. 28. The method of claim 27, wherein the method is maintained as: 29. 28. The method of claim 27, wherein the method is a continuous process. 30. Claim 27, wherein the reaction mixture is maintained at a temperature below about 30°C. How to put it on. 31. Halide-stabilized antimony trihalide is combined with Sb2O3 and concentrated HCl 28. The method of claim 27, wherein the reaction product is a mixture comprising: 32. 32. The method of claim 31, wherein the mixture comprises NaCl. 33. 32. The method of claim 31, wherein the mixture includes antimony metal. 34. 34. The method of claim 33, wherein the mixture comprises NaCl. 35. Halide-stabilized antimony trihalides contain antimony metal and concentrated H 28. The method of claim 27, wherein the reaction product is a reactant containing Cl. 36. 36. The method of claim 35, wherein the mixture contains excess NaCl. 37. Claim 1, wherein the trihalide is a complex containing (SbCl4)- ion. 24, 25, 26, 28, 29 or 31. 38. Trihalides include HSbCl4, NaSbCl4, HSbCl4hydrate , NaSbCl4hydrate and mixtures thereof. The method according to item 37. 39. The extracted SbsbS4 product is calculated by converting the chloride content of the product into the weight of the product. Claim 27, wherein the content is reduced to less than 300 ppm. the method of. 40. The withdrawn product and residual reaction mixture are transferred to a receiver containing aqueous NaCl. 28. The method of claim 27, wherein the process is carried out under continuous agitation. 41. A set containing SbSbS4 and halide-stabilized antimony trihalide A product. 42. Halide stabilized antimony trihalide is based on the weight of SbSbS4. 42. The composition of claim 41, wherein the composition is present in an amount within the range of 1 to 300 ppm . 43. Claim 41, wherein the antimony trihalide is antimony trichloride, or The composition according to item 42. 44. Claim 1, wherein the trihalide is a complex containing (SbCl4)- ion. The composition according to item 41 or 42.