Preparation method of calcium sulfonate with high calcium carbonate content

Abstract

The invention discloses a preparation method of calcium sulfonate with high calcium carbonate content, which comprises the following steps: adding an organic solvent, C1-C10 alcohol and calcium hydroxide into a reaction container, and uniformly stirring and mixing; then, dropwise adding a mixture consisting of petroleum sulfonic acid, heavy alkyl benzene sulfonic acid, long-chain alkyl benzene sulfonic acid and diluent oil into the reaction container; then, adding small-molecule C1-C3 carboxylic acid and at least one of an emulsifier and dodecenylsuccinic acid, heating to a preset temperature, and carrying out a neutralization reaction; after the neutralization reaction is finished, calcium hydroxide is added, and meanwhile carbon dioxide is introduced for a carbonization reaction; after the carbonization reaction is finished, diatomite is added for filtering and refining, and a high-base-number calcium sulfonate product with high calcium carbonate content is obtained. According to the invention, the calcium sulfonate product with the calcium carbonate content of more than 50% and clear and transparent appearance can be prepared.

Description

Technical Field

[0001] The invention relates to the technical field of lubricating oil additives, and in particular to a method for preparing calcium sulfonate with a high calcium carbonate content. Background Art

[0002] Increasingly stringent environmental emission requirements have placed more stringent requirements on the performance of lubricant additives, while internal combustion engine oils have also gradually become more high-end and multi-grade. In order to meet this lubrication demand, different proportions of calcium sulfonate additives are usually added to today's lubricants to meet the acid neutralization, cleaning, and calcium oxidation resistance of the compound. In order to meet the performance requirements, calcium sulfonate accounts for a high proportion in the compound package, which in turn results in poor product economics of the compound. Therefore, the development of a calcium sulfonate product with a high calcium carbonate content that meets the performance requirements and storage stability requirements of the compound can significantly reduce the proportion of calcium sulfonate in the compound, reduce production costs, and improve the market competitiveness of the product.

[0003] Due to its excellent acid neutralization ability, detergency, corrosion resistance and rust resistance, high base calcium sulfonate is widely used in industrial oil, internal combustion engine oil and other fields. High base calcium sulfonate is prepared by neutralization reaction and carbonation reaction of sulfonic acid and alkali under certain conditions. The raw materials for calcium sulfonate production are easy to obtain, and the product is biodegradable, which is in line with the current direction of environmental protection economic development.

[0004] Patent US4879053 proposes a method for preparing high-base calcium sulfonate, which uses calcium chloride and methanol as promoters to prepare high-base calcium sulfonate products of TBN300 and TBN400. Since calcium chloride is used as a promoter, a large amount of chloride ions will remain in the prepared product, which will cause corrosion to the metal surface during use and is not suitable for today's market demand. At the same time, the calcium carbonate content in TBN300 and TBN400 calcium sulfonate products is low. It is calculated that the calcium carbonate content in the TBN300 calcium sulfonate product is 300 / (56.1*2)*100 / 1000*100=26.74%; the calcium carbonate content in the TBN400 calcium sulfonate product is 400 / (56.1*2)*100 / 1000*100=35.65%.

[0005] Patent US6268318 proposes a method for preparing high-base calcium sulfonate by adding polyisobutylene succinic anhydride as a promoter during the reaction process. The total base number of the prepared product can reach 420, and the corresponding calcium carbonate content is 37.43%, which accounts for a relatively low proportion in the product.

[0006] Patent CN101318916B proposes a method for preparing a high-base calcium sulfonate of TBN300. This method uses alkylphenol salts, polyisobutylene succinic anhydride, low-carbon alcohols and other promoters to jointly promote the smooth progress of the reaction to obtain a TBN300 calcium sulfonate product, the corresponding calcium carbonate content of which is 26.74%.

[0007] The disadvantages of the prior art are:

[0008] 1. The total base number of calcium sulfonate prepared by the existing process is mainly concentrated in the range of 300 to 400, and the corresponding calcium carbonate content is 26.74 to 35.65%.

[0009] 2. The calcium carbonate content is low and the corresponding base number is low, resulting in a larger amount of calcium sulfonate added to the lubricating oil.

[0010] 3. It accounts for a high proportion in lubricant compounds, resulting in poor product economy of the compounds.

[0011] 4. When the calcium carbonate content reaches 40%, the product is very likely to become turbid and precipitate, causing the product quality to decline and the product to be unusable.

[0012] 5. The existing process cannot produce a calcium sulfonate product with a calcium carbonate content greater than 50% that meets the performance requirements. Summary of the invention

[0013] In view of the fact that the existing process cannot prepare a calcium sulfonate product with a calcium carbonate content greater than 50%, and the existing product is used in a large amount in a composite agent, resulting in high production cost of the composite agent and poor product economy, the present invention provides a method for preparing calcium sulfonate with a high calcium carbonate content.

[0014] The present invention discloses a method for preparing calcium sulfonate with a high calcium carbonate content, comprising:

[0015] Step 1, adding an organic solvent, a C1-C10 alcohol and calcium hydroxide into a reaction container, stirring and mixing evenly; then, dropping a mixture consisting of petroleum sulfonic acid, heavy alkylbenzene sulfonic acid, long-chain alkylbenzene sulfonic acid and diluent oil into the reaction container; then, adding a small molecule C1-C3 carboxylic acid and at least one of an emulsifier and dodecenylsuccinic acid, heating to a preset temperature for neutralization reaction;

[0016] Step 2: After the neutralization reaction is completed, calcium hydroxide is added and carbon dioxide is introduced to carry out a carbonization reaction;

[0017] Step 3: After the carbonization reaction is completed, diatomaceous earth is added for filtration and purification to obtain a high-basicity calcium sulfonate product with high calcium carbonate.

[0018] As a further improvement of the present invention, in step 1, the amount of each component added is, by weight:

[0019] 120-180 parts of organic solvent, 5-30 parts of C1-C10 alcohol, 5-15 parts of calcium hydroxide, 5-15 parts of petroleum sulfonic acid, 5-15 parts of heavy alkylbenzene sulfonic acid, 5-15 parts of long-chain alkylbenzene sulfonic acid, 20-40 parts of diluent oil, 1-10 parts of emulsifier, 1-10 parts of dodecenylsuccinic acid, and 1-10 parts of small molecule C1-C3 carboxylic acid.

[0020] As a further improvement of the present invention, in step 1, the temperature is raised to 60-70° C. for neutralization reaction, preferably raised to 65° C. for neutralization reaction.

[0021] As a further improvement of the present invention, the step 2 specifically comprises:

[0022] After the neutralization reaction is completed, calcium hydroxide is added in batches and carbon dioxide is introduced to carry out a carbonization reaction; wherein, the amount of calcium hydroxide added each time is 10 to 15 parts by weight; the ventilation rate of carbon dioxide is 120 to 180 ml / min, preferably 150 ml / min;

[0023] Specific:

[0024] After the neutralization reaction is completed, 10 to 15 parts of calcium hydroxide are added and a carbonization reaction is carried out by carbon dioxide; wherein the ventilation rate of carbon dioxide is 120 to 180 ml / min;

[0025] When the DBN of the reaction material reaches 35 to 45 (preferably 40) after the primary carbonization reaction, 10 to 15 parts of calcium hydroxide are added and carbon dioxide is introduced at the same ventilation rate for secondary carbonization reaction;

[0026] When the DBN of the reaction material reaches 35 to 45 (preferably 40) after the secondary carbonization reaction, 10 to 15 parts of calcium hydroxide are added and carbon dioxide is introduced at the same ventilation rate to carry out the tertiary carbonization reaction;

[0027] After three carbonization reactions until the DBN of the reaction material is 35-45 (preferably 40), 10-15 parts of calcium hydroxide are added and carbon dioxide is introduced at the same ventilation rate for a fourth carbonization reaction. After four carbonization reactions until the DBN of the reaction material is 10-15, the carbonization reaction is terminated.

[0028] As a further improvement of the present invention,

[0029] The organic solvent includes at least one of relatively polar solvents such as toluene and xylene, preferably xylene;

[0030] The alpha olefin used in the long-chain alkylbenzene sulfonic acid is C16-26, preferably C18-22;

[0031] The diluent oil includes at least one of 100N, 150SN and 150N base oils, and its amount is 0.9-1.6 times the amount of the total sulfonic acid;

[0032] The emulsifier includes at least one of monostearate, polyethylene glycol fatty acid ester, and Span 60;

[0033] The carboxylic acid is formic acid.

[0034] As a further improvement of the present invention, the alcohol is a mixed alcohol of methanol and octanol, and the emulsifier is a mixture of monostearate glyceride and polyethylene glycol fatty acid ester.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] The preparation method of the invention can prepare a calcium sulfonate product with a TBN of 600 to 650, and the corresponding calcium carbonate content is 53.48% to 57.93%; at the same time, the presence of the alkylbenzene sulfonic acid group ensures its oil solubility, stability, cleanliness, rust resistance and corrosion resistance in lubricating oil; the presence of a high content of calcium carbonate enables it to have good acid neutralization performance in lubricating oil; more than half of the prepared product contains calcium carbonate, and the product has a transparent appearance without turbidity. DETAILED DESCRIPTION

[0037] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention is clearly and completely described below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0038] The present invention is described in further detail below:

[0039] The present invention provides a method for preparing calcium sulfonate with a high calcium carbonate content, comprising:

[0040] Step 1, adding an organic solvent, a C1-C10 alcohol and calcium hydroxide into a reaction vessel equipped with a stirrer, a heating device and a thermometer, and stirring and mixing them evenly; then, dropping a mixture of petroleum sulfonic acid, heavy alkylbenzene sulfonic acid, long-chain alkylbenzene sulfonic acid and diluent oil into the reaction vessel; then, adding a small molecule C1-C3 carboxylic acid and at least one of an emulsifier and dodecenylsuccinic acid, and heating to 60-70° C. (preferably 65° C.) for neutralization reaction; wherein,

[0041] By weight, the amount of each component added is:

[0042] 120-180 parts of organic solvent, 5-30 parts of C1-C10 alcohol (monohydric or polyhydric alcohol with carbon chain length of C1-C10), 5-15 parts of calcium hydroxide, 5-15 parts of petroleum sulfonic acid, 5-15 parts of heavy alkylbenzene sulfonic acid, 5-15 parts of long-chain alkylbenzene sulfonic acid, 20-40 parts of diluent oil, 1-10 parts of emulsifier, 1-10 parts of dodecenylsuccinic acid, 1-10 parts of small molecule C1-C3 carboxylic acid;

[0043] Specific:

[0044] The organic solvent includes at least one of relatively polar solvents such as toluene and xylene, preferably xylene;

[0045] The alcohol is preferably a mixed alcohol of methanol and octanol;

[0046] The alpha olefin used in the long-chain alkylbenzene sulfonic acid is C16-26, preferably C18-22;

[0047] The diluent oil includes at least one of 100N, 150SN and 150N base oils, and its amount is 0.9-1.6 times the amount of the total sulfonic acid;

[0048] The emulsifier includes at least one of monostearate, polyethylene glycol fatty acid ester, and Span 60;

[0049] The carboxylic acid is preferably formic acid.

[0050] Step 2: After the neutralization reaction is completed, calcium hydroxide is added in batches and carbon dioxide is introduced to carry out a carbonization reaction; wherein, the amount of calcium hydroxide added each time is 10 to 15 parts by weight; the ventilation rate of carbon dioxide is 120 to 180 ml / min, preferably 150 ml / min;

[0051] Specific:

[0052] After the neutralization reaction is completed, 10 to 15 parts of calcium hydroxide are added and a carbonization reaction is carried out by carbon dioxide; wherein the ventilation rate of carbon dioxide is 120 to 180 ml / min; when the DBN of the reaction material is 35 to 45 (preferably 40) after the first carbonization reaction, 10 to 15 parts of calcium hydroxide are added and carbon dioxide with the same ventilation rate is introduced for a secondary carbonization reaction; when the DBN of the reaction material is 35 to 45 (preferably 40) after the second carbonization reaction, 10 to 15 parts of calcium hydroxide are added and carbon dioxide with the same ventilation rate is introduced for a tertiary carbonization reaction; when the DBN of the reaction material is 35 to 45 (preferably 40) after the tertiary carbonization reaction, 10 to 15 parts of calcium hydroxide are added and carbon dioxide with the same ventilation rate is introduced for a fourth carbonization reaction, and when the DBN of the reaction material is 10 to 15 after the fourth carbonization reaction, the carbonization reaction is terminated.

[0053] Step 3: After the carbonization reaction is completed, diatomaceous earth is added for filtration and purification to obtain a high-basicity calcium sulfonate product with high calcium carbonate.

[0054] The invention uses monoalkylbenzene sulfonic acid, dialkylbenzene sulfonic acid and petroleum sulfonic acid as main raw materials, and obtains a calcium sulfonate product with a high calcium carbonate content through neutralization reaction and carbonization reaction; the prepared calcium sulfonate product mainly consists of three parts: calcium carbonate, neutral calcium sulfonate and base oil, has a calcium carbonate content of more than 50%, and has a clear and transparent appearance; the calcium sulfonate product with a high calcium carbonate content has particularly strong acid neutralization ability, and has excellent detergency, antioxidant properties and the like, and can be widely used in various grades of industrial oils, internal combustion engine oils and marine oils.

[0055] Example 1: Preparation of a product with high calcium carbonate content Ca-1

[0056] Add 150g of xylene, 15g of methanol, and 12g of calcium hydroxide to the reactor and stir for 10min to mix evenly, then add a mixture of 10g of long-chain alkylbenzene sulfonic acid, 10g of heavy alkylbenzene sulfonic acid, 8g of petroleum sulfonic acid, and 30g of 100N base oil in 10min, then add 2g of dodecenylsuccinic acid and 1g of formic acid and heat to 65°C for neutralization reaction for 1h. After the neutralization reaction is completed, add 13g of calcium hydroxide and then carry out carbonization reaction. The carbon dioxide ventilation rate of the carbonization reaction is 150ml / min. When the DBN of the reaction material is controlled to be about 40, 13g of calcium hydroxide is added twice and ventilated at the same rate. When the DBN of the material is controlled to be about 40, 13g of calcium hydroxide is added three times and ventilation is continued. When the DBN of the material is controlled to be about 40, 13g of calcium hydroxide is added four times, and ventilation is continued until the DBN is controlled to be 10-15, and the carbonization reaction is completed. Diatomaceous earth was added for filtration, and the filtrate was subjected to reduced pressure distillation to obtain a product with a kinematic viscosity of 422 (100° C.), a calcium carbonate content of 39.39%, a total base number of 442, and a finished product turbidity of 52.8.

[0057] Example 2: Preparation of high calcium carbonate content product Ca-2

[0058] Add 150g of xylene, 15g of methanol, and 12g of calcium hydroxide to the reactor and stir for 10min to mix evenly, then add a mixture of 10g of long-chain alkylbenzene sulfonic acid, 10g of heavy alkylbenzene sulfonic acid, 8g of petroleum sulfonic acid, and 30g of 100N base oil in 10min, then add 3g of dodecenylsuccinic acid and 2g of formic acid and heat to 65°C for neutralization reaction for 1h. After the neutralization reaction is completed, add 13g of calcium hydroxide and then carry out carbonization reaction. The carbon dioxide ventilation rate of the carbonization reaction is 150ml / min. When the DBN of the reaction material is controlled to be about 40, 13g of calcium hydroxide is added twice and ventilated at the same rate. When the DBN of the material is controlled to be about 40, 13g of calcium hydroxide is added three times and ventilation is continued. When the DBN of the material is controlled to be about 40, 13g of calcium hydroxide is added four times, and ventilation is continued until the DBN is controlled to be 10-15, and the carbonization reaction is completed. Diatomaceous earth was added for filtration, and the filtrate was subjected to reduced pressure distillation to obtain a product with a kinematic viscosity of 365 (100° C.), a calcium carbonate content of 40.20%, a total base number of 451, and a finished product turbidity of 55.4.

[0059] Example 3: Preparation of high calcium carbonate content product Ca-3

[0060] Add 150g of xylene, 15g of methanol, and 12g of calcium hydroxide to the reactor and stir for 10min to mix evenly, then add a mixture of 10g of long-chain alkylbenzene sulfonic acid, 10g of heavy alkylbenzene sulfonic acid, 8g of petroleum sulfonic acid, and 30g of 100N base oil in 10min, then add 2g of dodecenylsuccinic acid, 2g of monostearate, and 1g of formic acid, and then warm up to 65°C for neutralization reaction for 1h. After the neutralization reaction is completed, add 13g of calcium hydroxide and then carry out carbonization reaction. The carbon dioxide ventilation rate of the carbonization reaction is 150ml / min. When the DBN of the reaction material is controlled to be about 40, 13g of calcium hydroxide is added twice and ventilated at the same rate. When the DBN of the material is controlled to be about 40, 13g of calcium hydroxide is added three times and ventilation is continued. When the DBN of the material is controlled to be about 40, 13g of calcium hydroxide is added four times, and ventilation is continued until the DBN is controlled to be 10-15, and the carbonization reaction is completed. Diatomaceous earth was added for filtration, and the filtrate was subjected to reduced pressure distillation to obtain a product with a kinematic viscosity of 323 (100° C.), a calcium carbonate content of 51.87%, a total base number of 582, and a finished product turbidity of 38.2.

[0061] Example 4: Preparation of high calcium carbonate content product Ca-4

[0062] Add 150g of xylene, 15g of methanol, 10g of octanol, and 12g of calcium hydroxide to the reactor and stir for 10min to mix evenly, then add a mixture of 10g of long-chain alkylbenzene sulfonic acid, 10g of heavy alkylbenzene sulfonic acid, 8g of petroleum sulfonic acid, and 30g of 100N base oil in 10min, then add 2g of polyethylene glycol fatty acid ester, 2g of monostearate, and 1g of formic acid, and then heat to 65°C for neutralization reaction for 1h. After the neutralization reaction is completed, add 13g of calcium hydroxide and then carry out carbonization reaction. The carbon dioxide ventilation rate of the carbonization reaction is 150ml / min. When the DBN of the reaction material is controlled to be about 40, add 13g of calcium hydroxide twice and ventilate at the same rate. When the DBN of the material is controlled to be about 40, add 13g of calcium hydroxide three times and continue to ventilate. When the DBN of the material is controlled to be about 40, add 13g of calcium hydroxide four times, and continue to ventilate until the DBN is controlled to be 10-15, and the carbonization reaction ends. Diatomaceous earth was added for filtration, and the filtrate was subjected to reduced pressure distillation to obtain a product with a kinematic viscosity of 318 (100° C.), a calcium carbonate content of 55.35%, a total base number of 621, and a finished product turbidity of 22.6.

[0063] Example 5: Preparation of high calcium carbonate content product Ca-5

[0064] Add 150g of xylene, 15g of methanol, 10g of octanol, and 12g of calcium hydroxide to the reactor and stir for 10min to mix evenly, then add a mixture of 10g of long-chain alkylbenzene sulfonic acid, 10g of heavy alkylbenzene sulfonic acid, 8g of petroleum sulfonic acid, and 30g of 100N base oil in 10min, then add 3g of polyethylene glycol fatty acid ester, 1g of monostearate, and 1g of formic acid, and then heat to 65°C for neutralization reaction for 1h. After the neutralization reaction is completed, add 13g of calcium hydroxide and then carry out carbonization reaction. The carbon dioxide ventilation rate of the carbonization reaction is 150ml / min. When the DBN of the reaction material is controlled to be about 40, add 13g of calcium hydroxide twice and ventilate at the same rate. When the DBN of the material is controlled to be about 40, add 13g of calcium hydroxide three times and continue to ventilate. When the DBN of the material is controlled to be about 40, add 13g of calcium hydroxide four times, and continue to ventilate until the DBN is controlled to be 10-15, and the carbonization reaction ends. Diatomaceous earth was added for filtration, and the filtrate was subjected to reduced pressure distillation to obtain a product with a kinematic viscosity of 339 (100° C.), a calcium carbonate content of 57.66%, a total base number of 647, and a finished product turbidity of 10.4.

[0065] Product performance evaluation comparison:

[0066] Calcium sulfonate was dissolved in 500N base oil at a concentration of 2%, stirred at 60°C for 2 hours, and a performance evaluation test was performed. The results are shown in Table 1.

[0067] Table 1

[0068]

[0069]

[0070] Comparison of performance evaluation experiments:

[0071] 1. The cleaning performance of the base oil is poor, the weight gain of the finished rubber board is very large, and the grade of the finished rubber board is poor.

[0072] 2. The calcium carbonate content of Ca-1 and Ca-2 is low, and the corresponding neutral soap content is high, and the corresponding detergency is better. The weight gain of the finished rubber board is about 45 mg, and the surface grade of the finished rubber board is 2.

[0073] 3. The calcium carbonate content of Ca-3, Ca-4 and Ca-5 is >50%, and the corresponding neutral soap content is low. The corresponding weight gain of the colloid board is about 50 mg, and the surface grade of the colloid board is 2.5. Overall, the cleanliness has decreased to a certain extent, but it is not obvious.

[0074] The calcium sulfonate prepared by this process achieves:

[0075] 1. A calcium sulfonate product with a high calcium carbonate content, which ensures its oil solubility, stability, cleanliness, rust resistance and corrosion resistance in lubricating oil; at the same time, the presence of high calcium carbonate content makes it have good acid neutralization performance in lubricating oil.

[0076] 2. The problem that the current process cannot produce products with a calcium carbonate content of >50% is solved. When the calcium carbonate content is >40%, the product is prone to turbidity and precipitation.

[0077] 3. The calcium carbonate content in the prepared calcium sulfonate is greater than 50%, which is a great breakthrough in calcium sulfonate detergent for lubricating oil.

[0078] 4. Provide guidance for the subsequent development of lubricant detergents to meet the needs of economic development.

[0079] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing calcium sulfonate with high calcium carbonate content, It is characterized in that include: Step 1, adding an organic solvent, a C1-C10 alcohol and calcium hydroxide into a reaction container, stirring and mixing evenly; then, dropping a mixture consisting of petroleum sulfonic acid, heavy alkylbenzene sulfonic acid, long-chain alkylbenzene sulfonic acid and diluent oil into the reaction container; then, adding a small molecule C1-C3 carboxylic acid and at least one of an emulsifier and dodecenylsuccinic acid, heating to a preset temperature for neutralization reaction; Step 2: After the neutralization reaction is completed, calcium hydroxide is added and carbon dioxide is introduced to carry out a carbonization reaction; Step 3: After the carbonization reaction is completed, diatomaceous earth is added for filtration and purification to obtain a high-basicity calcium sulfonate product with high calcium carbonate.

2. The method for preparing calcium sulfonate with high calcium carbonate content as claimed in claim 1, It is characterized in that In step 1, the added amount of each component is as follows: 120-180 parts of organic solvent, 5-30 parts of C1-C10 alcohol, 5-15 parts of calcium hydroxide, 5-15 parts of petroleum sulfonic acid, 5-15 parts of heavy alkylbenzene sulfonic acid, 5-15 parts of long-chain alkylbenzene sulfonic acid, 20-40 parts of diluent oil, 0-10 parts of emulsifier, 0-10 parts of dodecenylsuccinic acid, 1-10 parts of small molecule C1-C3 carboxylic acid.

3. The method for preparing calcium sulfonate with high calcium carbonate content as claimed in claim 1, It is characterized in that In the step 1, the temperature is raised to 60-70° C. for neutralization reaction.

4. The method for preparing calcium sulfonate with high calcium carbonate content as claimed in claim 1, It is characterized in that The step 2 specifically includes: After the neutralization reaction is completed, calcium hydroxide is added in batches and carbon dioxide is introduced to carry out carbonization reaction; wherein, the amount of calcium hydroxide added each time is 10 to 15 parts by weight; and the ventilation rate of carbon dioxide is 120 to 180 ml / min.

5. The method for preparing calcium sulfonate with high calcium carbonate content according to any one of claims 1 to 4, It is characterized in that The organic solvent includes at least one of toluene and xylene; The alpha olefin used in long-chain alkylbenzene sulfonic acid is C16-26; The diluent oil includes at least one of 100N, 150SN and 150N base oils, and its amount is 0.9-1.6 times the amount of the total sulfonic acid; The emulsifier includes at least one of monostearate, polyethylene glycol fatty acid ester, and Span 60; The carboxylic acid is formic acid.

6. The method for preparing calcium sulfonate with high calcium carbonate content as claimed in claim 5, It is characterized in that The alcohol is a mixture of methanol and octanol, and the emulsifier is a mixture of monostearate and polyethylene glycol fatty acid ester.

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