CN108017299B

CN108017299B - Grinding aid and application thereof

Info

Publication number: CN108017299B
Application number: CN201610967130.1A
Authority: CN
Inventors: 钱文斌
Original assignee: Hunan Changde Environment Technology Co ltd
Current assignee: Hunan Changde Environment Technology Co ltd
Priority date: 2016-10-28
Filing date: 2016-10-28
Publication date: 2020-05-15
Anticipated expiration: 2036-10-28
Also published as: CN108017299A

Abstract

The invention provides a grinding aid and application thereof, wherein the grinding aid contains waste liquid from caprolactam preparation by cyclohexanone. The grinding aid provided by the invention can recycle the waste liquid from the preparation of caprolactam from cyclohexanone, and has a good grinding effect.

Description

Grinding aid and application thereof

Technical Field

The invention relates to a grinding aid and application thereof.

Background

The building material is an important basic raw material industry supporting the social and economic development, wherein cement and concrete are indispensable basic materials for building engineering and various structures, and the building material has wide application, large consumption, stable performance and durability. Taking cement production as an example, the existing cement production process is 'two-mill one-burning', namely, grinding, calcining and cement finish grinding of raw materials. The devices for grinding are roller presses, vertical mills and ball mills, the energy consumed by the grinding process in the cement production process is very high, and the utilization rate of the energy is very low, so that the energy consumption of cement production per year is very large. In the modern cement industry, the building material grinding aid has become one of the effective measures for improving the grinding output efficiency, reducing the grinding power consumption, improving the cement strength, improving the building material performance and reducing the production cost in the production of cement and the like. Grinding aid is added in the grinding process of the building material, so that powder agglomeration can be prevented, ball wrapping is effectively weakened or prevented, and the grinding efficiency of the building material is improved; the quality of building materials can be improved, and the product grade is improved; can improve the utilization of waste materials such as fly ash, slag and the like, reduce the production cost such as the consumption of building material grinding bodies and the like, and save energy and resources.

The process for preparing caprolactam by oximation and rearrangement reaction of cyclohexanone also comprises a plurality of product refining steps such as extraction, back extraction, ion exchange, rectification and the like besides the two-step main reaction due to inorganic salts such as ammonium phosphate, ammonium sulfate, sodium nitrate and the like which are byproducts, and when the products are refined, respective waste liquid can be generated, for example, caprolactam and ammonium sulfate are refined by an extraction method, the extraction waste liquid can bring waste liquid containing chemical components of caprolactam and ammonium sulfate, the waste liquid is collectively called the waste liquid for preparing caprolactam from cyclohexanone, the national total amount of the waste liquid is about 50 ten thousand tons/year (with a concentration of 50 weight percent), COD is high, and biochemical treatment cannot be directly carried out. The currently widely adopted incineration method has the disadvantages of large investment, large energy consumption, certain environmental influence and resource waste.

Disclosure of Invention

The grinding aid provided by the invention can recycle waste liquid from the preparation of caprolactam from cyclohexanone and has a good grinding-aiding enhancement effect.

In order to achieve the aim, the invention provides a grinding aid which contains waste liquid from the preparation of caprolactam from cyclohexanone.

Preferably, the waste liquid from the production of caprolactam from cyclohexanone contains waste liquid from the production of cyclohexanone oxime from the oximation of cyclohexanone and/or waste liquid from the production of caprolactam from the rearrangement of cyclohexanone oxime.

Preferably, the waste liquid from the production of caprolactam from cyclohexanone contains 0.1-15 wt% of caprolactam, preferably 1-15 wt% of caprolactam.

Preferably, the waste liquid from the cyclohexanone production of caprolactam contains 2-60 wt% of inorganic salt, preferably 5-60 wt% of inorganic salt, wherein the inorganic salt comprises at least one selected from sodium nitrate, sodium sulfate, sodium thiocyanate, sodium chloride, sodium carbonate, ammonium nitrate and ammonium sulfate.

Preferably, the grinding aid also contains a pH value regulator, and the addition amount of the pH value regulator is based on the regulation of the pH value of the grinding aid to 7-14.

Preferably, the pH adjustor is at least one selected from the group consisting of lithium oxide, sodium oxide, potassium oxide, calcium oxide, magnesium oxide, aluminum oxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, and trisodium phosphate.

Preferably, the grinding aid also contains saponification waste lye generated by preparing cyclohexanone through oxidizing cyclohexane; wherein the weight ratio of the saponified waste lye to the waste liquid from the preparation of caprolactam from cyclohexanone is 100: (0-1000).

Preferably, the saponified spent lye contains 30 to 90% by weight of water, based on the weight of the saponified spent lye.

Preferably, the saponified spent lye contains 0.3 to 5% by weight of sodium hydroxide, based on the weight of the saponified spent lye.

Preferably, the process for preparing cyclohexanone by oxidizing cyclohexane is at least one selected from a cobalt salt catalytic oxidation method, a boric acid catalytic oxidation method, a titanium silicalite molecular sieve catalytic oxidation method and a catalyst-free oxidation method.

Preferably, the grinding aid further comprises a cement enhancing agent comprising at least one member selected from the group consisting of an alcamines additive, a sodium and/or calcium salt additive, a cyanamide additive, and a polyol ether additive.

Preferably, the alkanolamine additive accounts for 10-90 wt% of the grinding aid by weight, and is at least one selected from the group consisting of triethanolamine, triisopropanolamine, tricyclohexanolamine, diethanol monoisopropanolamine, diethanol monocyclohexanolamine, diisopropanol monoethanolamine, diisopropanol monocyclohexanolamine, dicyclohexylalcohol monoethanolamine and dicyclohexylalcohol monoisopropanolamine.

Preferably, the sodium salt and/or calcium salt additive accounts for 1-90 wt% of the grinding aid by weight, and the sodium salt and/or calcium salt additive is at least one selected from sodium thiocyanate, sodium phosphate, sodium chloride, calcium sulfate, calcium chloride, sodium fluorosilicate, sodium sulfate and sodium nitrate.

Preferably, the polyol ether additive comprises at least one selected from the group consisting of polyols, polyol ethers and sugars, the polyols comprise at least one selected from the group consisting of ethylene glycol, propylene glycol, glycerol, polyethylene glycol, triglycerol and polypropylene glycol, the polyol ethers comprise polyethylene glycol ethers and/or polypropylene glycol ethers, and the sugars comprise at least one selected from the group consisting of white sugar, glucose and molasses, in a proportion of 1 to 90% by weight, preferably 1 to 50% by weight, of the grinding aid.

Preferably, the cyanamide additive accounts for 10-90 wt% of the grinding aid, and the cyanamide additive comprises at least one selected from melamine, sulfonated melamine, cyanamide and tricyanamide.

Preferably, the grinding aid further comprises a defoamer; the defoaming agent accounts for 0.01-0.5 wt% of the grinding aid by weight, and comprises an organic silicon defoaming agent and/or a polyether modified silicon additive.

Preferably, the grinding aid further comprises a cement accelerator which is at least one selected from the group consisting of aluminum salts, magnesium salts, carbonates, and silica salts.

The invention also provides application of the grinding aid provided by the invention in cement, cement admixture or mineral product grinding.

The waste liquid from the preparation of caprolactam from cyclohexanone is used as a component of the grinding aid for recycling, so that the problem of reasonable treatment of the waste liquid from the preparation of caprolactam from cyclohexanone is solved, the purposes of cleanness, environmental protection, low cost and comprehensive utilization of resources are achieved, the grinding aid has a good grinding aid effect, the material flowability in the grinding process can be improved, the 45-micron screen residue is reduced, the specific surface area of the product obtained by grinding is improved, and the construction performance and the mechanical performance of final cement are not influenced.

Additional features and advantages of the invention will be set forth in the detailed description which follows.

Detailed Description

The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.

The invention provides a grinding aid, which contains waste liquid from caprolactam preparation by cyclohexanone.

According to the present invention, the grinding aid is well known to those skilled in the art, and may be used for grinding cement clinker, cement admixture and mineral products in an internal blending amount of 0.01 wt% to 0.3 wt% to improve the grinding efficiency and the properties of the ground product.

The cement clinker is a calcined product of a calcareous raw material taking calcium carbonate as a main component, and is used for preparing cement final powder after grinding, wherein the cement final powder is a product obtained by adding or not adding other mixed materials into the cement clinker and then grinding, and is a component for forming cement. The grinding aid of the invention can be used to prepare a variety of cement end powders, such as those used to prepare PO 42.5, PI42.5, or PC 32.5R cements. The calcareous material may be a material selected from limestone, marl, chalk, shells and corals. Wherein, the main mineral of the limestone is calcite, the pure limestone contains CaO about 56 percent and the loss on ignition is about 44 percent; the marlite is uniformly mixed sedimentary rock formed by simultaneously depositing calcium carbonate and clay, the main mineral of the marlite is calcite, the marlite generally comprises high-calcium marlite and low-calcium marlite, the CaO content of the high-calcium marlite is more than or equal to 45 weight percent, and the CaO content of the low-calcium marlite is less than 45 weight percent; the chalk is a substance formed by stacking marine organism shells and shells, and the main component of the chalk is calcium carbonate with the content of 80-90 wt%; the calcium carbonate content of the shell and coral raw materials is about 90 wt%.

The cement admixture can be added into the cement final powder after being ground to be used as a part of a cement product, or can be directly ground together with cement clinker to be used as the cement product, and the cement admixture can comprise one or more of fly ash, slag, volcanic ash, sandstone, quartz sand, clay, shale, gypsum, iron ore powder, kaolin and bauxite.

Mineral products generally refer to all natural minerals or rock resources which are buried underground (or distributed on the ground surface, or weathered rocks, or deposited rocks) and can be utilized by human beings, the mineral products can comprise phosphorite, iron ore, copper ore, gold ore, silver ore, titanium ore and the like, and the mineral products are ground to facilitate subsequent treatment.

China is a country with large consumption of building materials, cement is taken as an example, the total yield of the cement reaches 18 hundred million tons in 2011, and about 90 million tons of grinding aids are needed according to the fact that the dosage of the grinding aids accounts for 0.05 weight percent of the cement product.

According to the invention, grinding operation by adding grinding aid can adopt the conventional technical means in the field, for example, grinding for 20-40min by adopting a ball mill.

According to the invention, the waste liquid from the production of caprolactam from cyclohexanone can contain the waste liquid from the production of cyclohexanone oxime from the oximation of cyclohexanone and/or the waste liquid from the production of caprolactam from rearrangement of cyclohexanone oxime, preferably, the weight ratio of the waste liquid from the production of cyclohexanone oxime from the oximation of cyclohexanone to the waste liquid from the production of caprolactam from rearrangement of cyclohexanone oxime in the waste liquid from the production of caprolactam from cyclohexanone is (0-30): (70-100).

According to the present invention, cyclohexanone may be oximated with hydroxylamine or the like to produce cyclohexanone oxime, and the process may include at least one selected from the group consisting of raschig method (HSO method), nitric oxide method (NO method), hydroxylamine phosphate method (HPO method), and ammoximation method (HAO method), and for example, the specific process steps of ammoximation method may be represented by the following formula:

in the process of preparing cyclohexanone oxime by oximating cyclohexanone, acid-base salt wastewater is generated by a water phase and a cleaning filter, the wastewater is called waste liquid for preparing cyclohexanone oxime by oximating cyclohexanone, and the main components of the waste liquid are water and ammonium salts such as ammonium phosphate, sodium nitrate, sodium phosphate and the like.

According to the present invention, cyclohexanone oxime may be subjected to intramolecular rearrangement in the presence of sulfuric acid or oleum or a catalyst (e.g., a titanium silicalite molecular sieve) to obtain caprolactam, which is referred to as beckmann transposition rearrangement reaction. When fuming sulfuric acid is used, the fuming sulfuric acid is generally neutralized with ammonia water after rearrangement, and a large amount of ammonium sulfate is produced as a by-product. In order to improve the yield of caprolactam and ensure the quality, ammonium sulfate solution is extracted subsequently, and the caprolactam crude product generated by rearrangement is extracted and back-extracted, wherein solvents such as benzene and toluene are generally adopted for extraction. In addition, after extraction, the caprolactam is subjected to anion-cation exchange process to remove residual inorganic salts such as ammonium sulfate and the like. The waste liquid after extraction, the waste liquid after back extraction and the waste liquid after ion exchange, which are generated in the product refining steps, are called the waste liquid for preparing caprolactam through cyclohexanone-oxime rearrangement, and are called the waste liquid for oxime rearrangement for short. The waste liquid from caprolactam rearrangement production comprises main organic components such as caprolactam, o-cyclohexanediol, o-hydroxycyclohexanone, hexanal and the like, and main inorganic components such as sodium nitrate, ammonium sulfate, sodium thiocyanate and the like. The specific reaction process steps can be shown as follows:

according to the invention, the waste liquid from the production of caprolactam from cyclohexanone preferably contains 0.1-15 wt.% of caprolactam, 30-80 wt.% of water and 2-60 wt.% of inorganic salts, more preferably contains 1-15 wt.% of caprolactam, 30-80 wt.% of water and 5-60 wt.% of inorganic salts. The caprolactam contributes to the strength of the cement product, and the inorganic salt may include at least one selected from the group consisting of sodium nitrate, sodium sulfate, sodium thiocyanate, sodium chloride, sodium carbonate, ammonium nitrate, and ammonium sulfate.

According to the invention, the waste liquid from the preparation of caprolactam from cyclohexanone can be directly used as a grinding aid for grinding without any pretreatment, and the effect of adding the adjusting additive is better. The adjusting additive refers to a component which is added into the grinding aid and is helpful for improving grinding and enhancing effects, and the composition and the addition amount of the adjusting additive are not limited in the invention, and the adjusting additive can be added as a single component or a conventional grinding aid in the form of an additive. For example, the conditioning additive may include at least one selected from a pH adjuster, a cement enhancer, a defoamer, and a cement accelerator, and may further include at least one of urea, a lignin salt, and calcium formate, and other addable components known to those skilled in the art. The weight ratio of the waste liquid of caprolactam prepared from cyclohexanone to the regulating additive can be 100: (0-1000), preferably 100: (1-400).

According to the invention, because the waste liquid from the preparation of caprolactam from cyclohexanone contains excessive acid, in order to avoid adverse effects on the construction strength of building materials such as cement and to improve the grinding effect, a pH value regulator can be added into the waste liquid from the preparation of caprolactam from cyclohexanone to regulate the pH value of a grinding aid, the addition amount of the pH value regulator is not particularly limited, and the pH value of the grinding aid can be regulated to 7-14. The composition of the pH adjuster is not particularly limited in the present invention, and may be, for example, oxides and hydroxides corresponding to alkali metals and alkaline earth metals, and salts of weak acids such as carbonic acid, phosphoric acid, and acetic acid, and is preferably at least one selected from the group consisting of lithium oxide, sodium oxide, potassium oxide, calcium oxide, magnesium oxide, aluminum oxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, and trisodium phosphate.

According to the invention, the process for preparing cyclohexanone by oxidizing cyclohexane is researched more since the industrialization in 1961. According to different catalysts, including cobalt salt catalytic oxidation, boric acid catalytic oxidation, titanium silicalite catalytic oxidation and catalyst-free oxidation, although the technological processes have various characteristics, the basic principle and the reaction flow are the same, and the specific reaction flow can be shown as the following formula:

in the first step, cyclohexane is oxidized with an oxidizing agent (e.g., oxygen) in the presence or absence of a catalyst to form cyclohexyl hydroperoxide. For example, the reaction temperature is 160 ℃, the pressure is about 1.08MPa, 5 kettles are connected in series for reaction for 1h, the conversion rate of cyclohexane is controlled to be about 5 weight percent by contacting with air, and the selectivity of cyclohexyl hydroperoxide is about 95 weight percent.

In the second step, alkali, such as sodium hydroxide solution, is added into the product obtained in the first step, the function of the alkali is to decompose peroxide, and cobalt naphthenate with the weight of 0-10ppm relative to the weight of the reaction liquid can be added to catalyze and promote the decomposition of cyclohexyl hydroperoxide according to the process condition, so that cyclohexanone is obtained

And cyclohexanol

Mainly organic phase and water phase, namely saponification waste lye.

The saponified waste lye is generally a black liquid or a liquid containing a portion of solids, and has a density of generally 1.05 to 1.25 g/ml, and may contain 30 to 90% by weight of water, 0.3 to 5% by weight of sodium hydroxide, salts, organic substances, etc., based on the weight of the saponified waste lye. The grinding aid can also contain saponified waste lye; wherein the weight ratio of the saponification waste lye to the waste liquid of the caprolactam preparation from cyclohexanone can be 100: (0-1000), preferably 100: (1-400).

According to the present invention, the cement reinforcing agent may include at least one selected from the group consisting of an alcamines additive, a sodium and/or calcium salt additive, a cyanamide additive, and a polyol ether additive.

According to the invention, the alcohol amine additive is helpful for eliminating static electricity, improving grinding effect and improving product strength, the proportion of the alcohol amine additive in the grinding aid can be 10-90 wt%, and the alcohol amine additive can be at least one selected from triethanolamine, triisopropanolamine, tricyclohexylamine, diethanol monoisopropanolamine, diethanol monocyclohexanolamine, diisopropanol monoethanolamine, diisopropanol monocyclohexanolamine, dicyclohexylethanolamine and dicyclohexylalcohol monoisopropanolamine.

According to the present invention, the sodium salt and/or calcium salt additive can improve the grindability and fluidity of building materials and minerals and enhance the strength of cement products. The grinding aid comprises a grinding aid, a sodium salt and/or calcium salt additive and a grinding aid, wherein the sodium salt and/or calcium salt additive accounts for 1-90 wt% of the grinding aid by weight, and the sodium salt and/or calcium salt additive can be at least one selected from sodium thiocyanate, sodium phosphate, sodium chloride, calcium sulfate, calcium chloride, sodium fluosilicate, sodium sulfate and sodium nitrate.

According to the invention, the polyol ether additive is helpful for eliminating static electricity, improving the grinding effect and improving the strength of cement products. The proportion of the grinding aid additive by weight may be 1-90 wt%, preferably 1-50 wt%, based on the grinding aid, and the polyol ether additive may include at least one selected from the group consisting of polyols, polyol ethers, and sugars, the polyols may include at least one selected from the group consisting of ethylene glycol, propylene glycol, glycerol, polyethylene glycol, triglycerol, and polypropylene glycol, the polyol ethers may include polyethylene glycol ethers and/or polypropylene glycol ethers, and the sugars may include at least one selected from the group consisting of white sugar, glucose, and molasses.

According to the invention, the cyanamide additive is helpful for eliminating static electricity, improving grinding effect and improving the strength of cement products, the proportion of the cyanamide additive in the grinding aid can be 10-90 wt%, and the cyanamide additive can comprise at least one selected from melamine, sulfonated melamine, cyanamide and tricyanamide.

According to the invention, the defoaming agent can be used for reducing the surface tension of the grinding aid, inhibiting the generation of foam or eliminating the generated foam, thereby improving the grinding aid effect. The defoaming agent accounts for 0.01-0.5 wt% of the grinding aid, the defoaming agent can comprise a silicone defoaming agent and/or a polyether modified silicone additive, the silicone defoaming agent can be at least one selected from polydimethylsiloxane, fluorosilicone and ethylene glycol siloxane, and can also be a special defoaming agent for commercially available concrete, such as building material industry defoaming agents of Dongguan Defeng defoaming agent company Limited, and product models of 'DF-179' and 'DF-175'.

According to the invention, the grinding aid may also contain a cement accelerator, which may be at least one selected from the group consisting of aluminum salts, magnesium salts, carbonates, and silica salts.

The invention will be further illustrated by the following examples, but is not to be construed as being limited thereto.

In the embodiment of the invention, the waste liquid obtained by preparing caprolactam from cyclohexanone is marked as liquid C, which is obtained from a corresponding production device of caprolactam division of Barring division of petrochemical group of China, and comprises 10 wt% of waste liquid (marked as liquid C1) obtained by oximation of cyclohexanone to prepare cyclohexanone oxime and 90 wt% of waste liquid (marked as liquid C2) obtained by rearrangement of cyclohexanone oxime to prepare caprolactam. The specific properties of the liquid C are as follows: the relative density is 1.16 g/cubic centimeter, the content of ammonium nitrate is 14 weight percent, the content of ammonium sulfate is 10 weight percent, the content of sodium thiocyanate is 11 weight percent, the content of caprolactam is 6 weight percent, the content of water is 55 weight percent, and the balance is impurities such as sodium fatty acid, paraffin oil, organosilicon and the like.

In the embodiment of the invention, saponified waste alkali liquor is taken from saponified waste alkali liquor generated in a cyclohexane oxidation device of caprolactam division of the department of the country petrochemical group, holy division, on 2016 (6 months and 3 days), and a process for preparing cyclohexanone by cyclohexane oxidation is a catalyst-free oxidation method, marked as solution A, and has the following properties: the relative density was 1.197 g/cc, the water content was 42 wt% and the sodium hydroxide content was 2 wt%.

The conditioning additives used in the examples were: sodium hydroxide, potassium hydroxide, sodium carbonate, triethanolamine, triglycerol, and the like, are commercially available.

The embodiment and the comparative example of the invention adopt a method in national standard GB/T26748-.

The grinding in the embodiment and the comparative example of the invention is carried out in a national standard cement test small mill which accords with the grinding-aid effect experimental method in GB/T26748-.

The comparative example DA1 and examples SA1-SA5 illustrate the effect of using only C liquor as a cement grinding aid on the grinding efficiency of cement clinker.

Comparative example DA1

Cement clinker (commercial PI cement), slag (martensite steel group) and phosphate ore (Jingmen Jingxiang phosphate ore mining company) were ground separately, and the specific conditions and results are shown in tables 1-3.

Example SA1-SA5

The liquid C is mixed with cement clinker (commercial grade is PI cement), slag (Martin group) and phosphorite (Jingmen's Jingxiang phosphorite mining company) in different weight proportions to be ground respectively, and specific conditions and results are shown in tables 1-3.

Table 1: cement clinker grinding conditions and results of comparative example DA1 and examples SA1-SA5

Table 2: slag milling conditions and results for comparative example DA1 and example SA1-SA5

Table 3: ground phosphate rock conditions and results for comparative example DA1 and examples SA1-SA5

As can be seen from the results of tables 1-3: 1. after the liquid C is added, the fluidity of all materials is improved; 2. after the liquid C is added, the 45 micron screen residue of all materials is reduced; 3. after the addition of the liquid C, the specific surface areas of the materials in the examples SA1-SA5 are all increased, but excessive addition of the liquid C can greatly improve the flowability of the materials, reduce the friction force between the materials and a grinding medium, prevent the materials from being effectively ground, increase the screen residue and reduce the specific surface area. These results show that the liquid C has good grinding-aiding effect on cement clinker, slag and phosphate rock.

Examples SB1-SB4 illustrate the effect of using liquor C (100 parts by weight), with and without the addition of conditioning additives, as a cement grinding aid on the grinding efficiency of cement clinker which is used in examples SB1-SB4 under the trade designation PI.

Example SB1

And (3) taking the liquid C as a grinding aid, and mixing cement clinker in a proportion of 0.05 weight percent respectively for grinding treatment, wherein specific conditions and results are shown in a table 4.

Example SB2

And adding sodium hydroxide into the solution C to adjust the pH value to 10, then using the solution C as a grinding aid, and mixing cement clinker in a proportion of 0.05 wt% respectively to perform grinding treatment, wherein specific conditions and results are shown in Table 4.

Example SB3

And adding potassium hydroxide into the solution C to adjust the pH value to 10, adding 40 parts by weight of triethanolamine and 30 parts by weight of the solution A as grinding aids, and respectively adding cement clinker into the solution C in a proportion of 0.05 weight percent to perform grinding treatment, wherein specific conditions and results are shown in Table 4.

Example SB4

Adding sodium carbonate into the solution C to enable the pH value to be 10, adding 30 parts by weight of triethanolamine, 25 parts by weight of the solution A and 15 parts by weight of triglycerin to serve as grinding aids, and respectively adding cement clinker in a proportion of 0.05 weight percent for grinding treatment, wherein specific conditions and results are shown in Table 4.

Table 4: grinding conditions and results of examples SB1-SB4

Examples	Amount of cement (g)	Grinding time (min)	45 μm screen (%)	Specific surface area (m)²/kg)
					SB1	5000	33	5.0	367
SB2	5000	33	4.5	376
					SB3	5000	33	4.0	387
SB4	5000	33	3.8	396

As can be seen from the results in table 4: after the adjusting additive is added into the liquid C for optimization, the 45-micron screen residue of all the materials is reduced and the specific surface area is increased, which shows that the liquid C has the optimization effect after the adjusting additive is added.

Comparative example DC1

Comparative example DC1 construction performance of a cement product with the trade name PO 42.5 was determined by the test method Standard for the Performance of ordinary concrete mixture containing national Standard GB/T50080 and 2002 of the people's republic of China, and specific test conditions and results are shown in Table 5.

Examples SC1-SC4

Examples SC1-SC4 illustrate the influence of the liquid C and the liquid C containing a regulating additive on the cement construction performance, the grinding aid in the examples SB1-SB4 is added into a cement product in a proportion of 0.05 weight percent, the brand number of the used cement product is PO 42.5, the specific test method is shown in the national standard GB/T50080 and 2002 standard for the performance test method of the common concrete mixture of the people's republic of China, and the specific test conditions and results are shown in Table 5.

Table 5: comparative example DC1 and examples SC1-SC4 demonstrate the effect of liquid C on Cement workability

As can be seen from the results in Table 5, the addition of the liquid C increases the water consumption for the standard consistency of the cement, shortens the setting time, slightly increases or maintains the influence on the mobile phase of the mortar, and both meet the national standard.

Comparative examples DD1-DD3

The cement mechanical properties of the comparative examples DD1-DD3 with the trade marks of PI 52.5, PO 42.5 and PC 32.5R are measured, the specific test method is shown in the national standard GB/T50081-2002 standard for testing the mechanical properties of the common concrete of the people's republic of China, and the specific test conditions and results are shown in Table 6.

Examples SD1-SD3

Examples SD1-SD3 illustrate the influence of liquid C on the mechanical properties of cement, the grinding aid of example SB4 is added into cement in an amount of 0.05 wt%, the grades of the used cement are PI 52.5, PO 42.5 and PC 32.5R, the specific test method is shown in the national Standard of the people's republic of China GB/T50081-2002 standard for testing the mechanical properties of common concrete, and the specific test conditions and results are shown in Table 6.

Table 6: comparative examples DD1-DD3 and examples SD1-SD3 demonstrate the effect of liquid C on Cement workability

As can be seen from the results in Table 6, the cement strength changes after the grinding aid is added are different due to different cements, so that the compressive strength of cement mortar at all ages is increased and the compressive strength meets the requirements of national standard regulations.

Example SE1-SE3

The C1 liquid and C2 liquid are respectively mixed with cement clinker (commercial mark is PI cement), slag (Marangni group) and phosphate rock (Jingmen Jingxiang phosphate rock mining company) and are respectively ground, and specific conditions and results are shown in Table 7.

Table 7: grinding conditions and results for examples SE1-SE3

As can be seen from table 7, the single use of C1 liquid and the single use of C2 liquid for the grinding treatment also has good grinding effect.

Although the invention has been described in detail hereinabove by way of general description, specific embodiments and tests, it will be apparent to those skilled in the art that modifications and improvements can be made thereto or known or even established grinding aid ingredients, such as polycarboxylates, lignosulfonates, polyacrylamides, can be added based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims

1. A grinding aid, which contains waste liquid from the preparation of caprolactam from cyclohexanone; the waste liquid from the preparation of caprolactam from cyclohexanone contains waste liquid from the preparation of cyclohexanone oxime by oximation of cyclohexanone and/or waste liquid from the preparation of caprolactam by rearrangement of cyclohexanone oxime; the waste liquid from the preparation of caprolactam from cyclohexanone contains caprolactam and inorganic salt; the inorganic salt includes at least one selected from the group consisting of sodium nitrate, sodium sulfate, sodium thiocyanate, sodium chloride, sodium carbonate, ammonium nitrate and ammonium sulfate.

2. The grinding aid of claim 1, wherein the waste liquid from the production of caprolactam from cyclohexanone contains 0.1-15 wt% of caprolactam, based on weight.

3. The grinding aid of claim 1, wherein the waste liquid from cyclohexanone to caprolactam contains 2-60 wt% of the inorganic salt.

4. The grinding aid of claim 1, wherein the grinding aid further comprises a pH adjusting agent added in an amount to adjust the pH of the grinding aid to a range of 7 to 14.

5. The grinding aid of claim 4 wherein the pH adjuster is at least one selected from the group consisting of lithium oxide, sodium oxide, potassium oxide, calcium oxide, magnesium oxide, aluminum oxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, and trisodium phosphate.

6. The grinding aid of claim 1 wherein the grinding aid further comprises saponified spent lye from oxidation of cyclohexane to cyclohexanone; wherein the weight ratio of the saponified waste lye to the waste liquid from the preparation of caprolactam from cyclohexanone is 100: (0-1000).

7. The grinding aid of claim 6 wherein the saponified spent caustic solution contains 30-90% water by weight and based on the weight of the saponified spent caustic solution.

8. The grinding aid of claim 6 wherein the saponified spent caustic solution contains 0.3 to 5 weight percent sodium hydroxide, based on the weight of the saponified spent caustic solution.

9. The grinding aid of claim 6 wherein the process for preparing cyclohexanone by oxidation of cyclohexane is at least one selected from the group consisting of cobalt salt catalytic oxidation, boric acid catalytic oxidation, titanium silicalite catalytic oxidation, and catalyst-free oxidation.

10. The grinding aid of claim 1 further comprising a cement enhancing agent comprising at least one member selected from the group consisting of an alcamines additive, a sodium and/or calcium salt additive, a cyanamide additive, and a polyol ether additive.

11. The grinding aid of claim 10 wherein the proportion of the alkanolamine additive is 10-90% by weight of the grinding aid, the alkanolamine additive being at least one selected from the group consisting of triethanolamine, triisopropanolamine, tricyclohexylamine, diethanolisopropanolamine, diethanolisocyclolamine, diisopropanolamine, dicyclohexylamine monoethanolamine, and dicyclohexylamine monoisopropanolamine.

12. The grinding aid of claim 10 wherein the grinding aid comprises 1-90% by weight of the sodium and/or calcium salt additive, the sodium and/or calcium salt additive being at least one selected from the group consisting of sodium thiocyanate, sodium phosphate, sodium chloride, calcium sulfate, calcium chloride, sodium fluorosilicate, sodium sulfate and sodium nitrate.

13. A grinding aid as claimed in claim 10 wherein the proportion of said polyol ether additive is 1-90% by weight of said grinding aid, said polyol ether additive comprising a polyol ether, said polyol ether comprising a polyethylene glycol ether and/or a polypropylene glycol ether.

14. A grinding aid as claimed in claim 10 wherein the proportion of cyanamide additive to the grinding aid is from 10 to 90% by weight, the cyanamide additive comprising at least one member selected from melamine, sulfonated melamine, cyanamide and tricyanamide.

15. The grinding aid of claim 1 wherein the grinding aid further comprises an antifoaming agent; the defoaming agent accounts for 0.01-0.5 wt% of the grinding aid by weight, and comprises an organic silicon defoaming agent and/or a polyether modified silicon additive.

16. The grinding aid of claim 1 further comprising a cement accelerator which is at least one selected from the group consisting of aluminum salts, magnesium salts, and silicon salts.

17. Use of a grinding aid of any one of claims 1 to 16 in cement, cement admixtures, or mineral mills.