阅读说明：本技术 一种间苯二酚蒸馏残渣资源化利用的方法 (Method for resource utilization of resorcinol distillation residues ) 是由 马丽涛 董翠平 乔琼琼 宋宝 徐培洋 刘子恒 杨道顺 于 2020-10-27 设计创作，主要内容包括：本发明公开了一种间苯二酚蒸馏残渣资源化利用的方法,包括如下步骤：1)称取纯净水于反应釜I内,加热至40℃,加入对氨基苯磺酸钠、苯酚、尿素、蒸馏残渣,搅拌混合均匀,溶解完全后继续加热,加入氢氧化钠,搅拌混合均匀后,开始缓慢滴加甲醛,滴加完毕后升温并保温；保温结束后,加入后补水,降温记为母液A；2)称取纯净水于反应釜II内,边搅拌变缓慢加入磺化剂、间苯二酚蒸馏残渣,参照上述流程制得母液B；3)根据复配液用途,将母液A、母液B复配成不同配比的复配液。本发明具有操作简便、反应条件易于控制、生产工艺简单、无“三废”排出的优点,既解决了间苯二酚蒸馏残渣难处理问题,又实现资源循环利用。(The invention discloses a method for recycling resorcinol distillation residues, which comprises the following steps: 1) weighing purified water in a reaction kettle I, heating to 40 ℃, adding sodium sulfanilate, phenol, urea and distillation residues, stirring and mixing uniformly, continuing to heat after complete dissolution, adding sodium hydroxide, stirring and mixing uniformly, starting to dropwise add formaldehyde slowly, heating after dropwise addition is finished, and keeping the temperature; after the heat preservation is finished, adding post-supplement water, and cooling and marking as mother liquor A; 2) weighing purified water in a reaction kettle II, slowly adding a sulfonating agent and resorcinol distillation residues while stirring, and preparing a mother solution B according to the above flow; 3) according to the use of the compound liquid, the mother liquid A and the mother liquid B are compounded into compound liquids with different proportions. The method has the advantages of simple and convenient operation, easy control of reaction conditions, simple production process and no discharge of three wastes, solves the problem of difficult treatment of the resorcinol distillation residues, and realizes the cyclic utilization of resources.)

1. A method for resource utilization of resorcinol distillation residues is characterized by comprising the following steps:

1) weighing 400 parts of purified water 200-plus in a reaction kettle I according to the mass ratio, heating to 40 ℃, sequentially adding 190 parts of sodium sulfanilate, 40-105 parts of phenol, 5-25 parts of urea and 20-130 parts of resorcinol distillation residue, stirring and mixing uniformly, continuously heating to 60 ℃ after complete dissolution, adding sodium hydroxide to adjust the pH value of the solution to 9, stirring and mixing uniformly, starting to slowly dropwise add 200 parts of formaldehyde I solution 100-plus, heating to 90-95 ℃ after dropwise addition, and keeping the temperature for 2-4 h; after the heat preservation is finished, supplementing 200 portions of 100 plus water into the reaction kettle I, and cooling to below 70 ℃ for later use to be marked as mother liquor A;

2) weighing 500 parts of purified water 300-plus material in a reaction kettle II, slowly adding 165 parts of sulfonating agent 130-plus material and 15-50 parts of resorcinol distillation residue while stirring, heating to 40 ℃ after uniformly stirring and mixing, adding sodium hydroxide to adjust the pH value of the solution to 9, slowly dropwise adding 90-110 parts of acetone, and preserving heat for 0.5-1.5h after dropwise adding; after the heat preservation is finished, starting to dropwise add 200-plus 300 parts of formaldehyde I solution, after the dropwise addition is finished, heating to 90-95 ℃ and preserving the heat for 2-4 h; after the heat preservation is finished, cooling to below 70 ℃ for later use, and recording as mother liquor B;

3) according to the use of the compound liquid, the mother liquid A and the mother liquid B are compounded into compound liquids with different proportions.

2. The method for recycling the resorcinol distillation residue according to claim 1, wherein: in the step 1), weighing 350 parts of purified water according to the mass ratio, placing the purified water in a reaction kettle I, heating the mixture to 40 ℃, sequentially adding 150 parts of sulfanilic acid sodium salt, 40-105 parts of phenol, 5-25 parts of urea and 20-130 parts of resorcinol distillation residue, stirring and mixing the mixture uniformly, continuing to heat the mixture to 60 ℃ after complete dissolution, adding sodium hydroxide to adjust the pH value of the solution to 9, starting to slowly dropwise add 130 parts of formaldehyde I solution after uniform stirring and mixing, heating the solution to 90-95 ℃ after the dropwise addition is finished, and keeping the temperature for 3 hours; and after the heat preservation is finished, adding 165 parts of purified water into the reaction kettle I, and cooling to below 70 ℃ for later use to be recorded as mother liquor A.

3. The method for recycling the resorcinol distillation residue according to claim 1, wherein: in the step 2), weighing 360 parts of purified water according to the mass ratio, adding 140 parts of sulfonating agent and 20 parts of resorcinol distillation residue slowly while stirring, heating to 40 ℃ after uniformly stirring and mixing, adding sodium hydroxide to adjust the pH value of the solution to 9, slowly dropwise adding 96 parts of acetone, and keeping the temperature for 1h after dropwise adding; starting to dropwise add 268 parts of formaldehyde II solution after the heat preservation is finished, heating to 90-95 ℃ after the dropwise addition is finished, and preserving the heat for 3 hours; and after the heat preservation is finished, cooling to below 70 ℃ for later use, and recording as mother liquor B.

4. The method for recycling the resorcinol distillation residue according to claim 1, wherein: in the step 3), when the compound liquid is used as a cement water reducing agent, the mother liquid A and the mother liquid B are mixed according to the ratio of 5: 3, compounding; when the compound liquid is used as a coal slurry additive, the mother liquid A and the mother liquid B are mixed according to the ratio of 1: 9, compounding.

5. The method for recycling the resorcinol distillation residue according to claim 1, wherein: the dripping time of the formaldehyde I solution is 1.5-3h, the dripping time of the formaldehyde II solution is 1.5-4h, and the temperature in the dripping process is not more than 80 ℃; the formaldehyde I solution and the formaldehyde II solution are 35-37% of formaldehyde solutions in mass fraction.

6. The method for recycling the resorcinol distillation residue according to claim 1, wherein: the sulfonating agent is at least one of sodium sulfite, sodium bisulfite and sodium pyrosulfite.

7. The method for recycling the resorcinol distillation residue according to claim 1, wherein: the temperature of the acetone is not more than 55 ℃ in the dropping process, and the dropping time is 20-40 min.

8. The method for recycling the resorcinol distillation residue according to claim 1, wherein: the molar ratio of the sulfonating agent to the acetone is 0.3-0.68: the molar ratio of the formaldehyde I solution to the acetone is 1.6-2: 1.

Technical Field

The invention relates to the technical field of chemical industry, in particular to a method for recycling resorcinol distillation residues.

Background

The water reducing agent is used as the most additive for concrete, can reduce the water consumption in concrete mixtures, and has a good effect on improving the concrete performance of concrete. Compared with polycarboxylic acid high-performance water reducing agents, the naphthalene water reducing agent, the aliphatic water reducing agent and the sulfamic acid high-efficiency water reducing agent have much poorer water reducing and collapse protecting performances due to the defects of the structures, and have wide raw material sources, relatively lower cost, better adaptability and wider application. However, the price of raw materials such as acetone and sodium sulfite is greatly increased at present, so that the search for new raw materials with lower cost is imperative. In recent years, with the increasing awareness of environmental protection and the increasing awareness of health hazards due to formaldehyde emission from building materials in the environment of long-term living and living, more and more building companies have selected green and environmentally friendly polycarboxylic acid water reducers and the market of second-generation water reducers (naphthalene water reducers, sulfamic acid water reducers, and aliphatic water reducers) has been decreasing because naphthalene water reducers, sulfamic acid water reducers, and aliphatic water reducers contain or emit unreacted free formaldehyde.

Resorcinol is a key raw material for producing synthetic resin, adhesives, dyes, medicines, ultraviolet absorbers, photosensitive film primer, explosives, cosmetics and the like, and is widely applied. Domestic enterprises mostly adopt a classical synthesis process, namely a benzenesulfonic acid method: benzene is sulfonated to synthesize m-benzene disulfonic acid, sodium hydroxide is used for alkali fusion to generate resorcinol sodium, resorcinol sodium is neutralized by acid to obtain resorcinol crude product, and then the product is refined by extraction and distillation. During the distillation purification, a large amount of distillation residues which are difficult to handle are generated. The residue was dark reddish brown solid, shiny and had a strong phenolic smell. The main components of the waste residue are classified compounds such as 2,3 ', 4-trihydroxy biphenyl, accounting for 30-50% of the total amount of the waste residue, and in addition, a small amount of resorcinol, a small amount of 3, 4' -dihydroxy biphenyl, a plurality of polyhydroxy isomers and polymers are also provided, the waste residue contains abundant phenolic hydroxyl groups, has similar properties with phenols, is dissolved in alkali liquor, and is partially dissolved in water. The waste residue has large discharge amount and high toxicity, and pollution caused by poor management threatens human health, so that great attention is paid at home and abroad. The resorcinol treatment is very difficult, the cost is very expensive, the extraction process is complex, and the extraction efficiency is low.

In the prior art, research reports on the analysis and utilization of resorcinol waste residues mainly utilize the waste residues to prepare concrete composite additives, sealants, lubricants and the like, such as:

miller et al, in the patent Acid-resistant molded base casting organic fibers, resorcinol resins, and aspHalt [ P ]. US, mix the slag, organic fibers and aspHalt as Acid-resistant building materials, e.g., a material prepared by mixing 53 parts of aspHalt, 12.5 parts of fiber, 3 parts of resorcinol slag, and 31.5 parts of filler, to a depth of 7/64 inches.

PausK.F. in patent Complex additive for a concrete mix [ P ] US, a concrete composite additive is synthesized from resorcinol waste slag. The composite additive is synthesized by using 9.5-10.0% of waste slag, 5.8-8.0% of sodium hydroxide and 0.78-0.98% of formaldehyde and water, and has good plasticizing function.

JP patent Resins for adhesives, which use the waste residues, formaldehyde and sodium hydroxide to synthesize phenolic Resins at 80 ℃, and the addition of nut powder, water and paraformaldehyde makes them useful as adhesives for plywood production with good adhesive properties.

Disclosure of Invention

The invention aims to overcome the problems in the prior art and provide a method for recycling resorcinol distillation residues, wherein a small amount of polyhydroxy polymers or isomers such as resorcinol, 2, 3', 4-trihydroxy biphenyl and the like in the resorcinol distillation residues are easily subjected to substitution reaction with formaldehyde due to more very active ortho-position hydrogen under an alkaline condition, so that a sulfonated acetone-formaldehyde condensate is subjected to graft modification, the content of free formaldehyde in a final product can be reduced, the release of the free formaldehyde is prevented, the toxicity of the product is reduced, and the harm to the environment and the human body is reduced.

In order to achieve the technical purpose and achieve the technical effect, the invention is realized by the following technical scheme:

a method for resource utilization of resorcinol distillation residues comprises the following steps:

1) weighing 400 parts of purified water 200-plus in a reaction kettle I according to the mass ratio, heating to 40 ℃, sequentially adding 190 parts of sodium sulfanilate, 40-105 parts of phenol, 5-25 parts of urea and 20-130 parts of resorcinol distillation residue, stirring and mixing uniformly, continuously heating to 60 ℃ after complete dissolution, adding sodium hydroxide to adjust the pH value of the solution to 9, stirring and mixing uniformly, starting to slowly dropwise add 200 parts of formaldehyde I solution 100-plus, heating to 90-95 ℃ after dropwise addition, and keeping the temperature for 2-4 h; after the heat preservation is finished, supplementing 200 portions of 100 plus water into the reaction kettle I, and cooling to below 70 ℃ for later use to be marked as mother liquor A;

2) weighing 500 parts of purified water 300-plus material in a reaction kettle II, slowly adding 165 parts of sulfonating agent 130-plus material and 15-50 parts of resorcinol distillation residue while stirring, heating to 40 ℃ after uniformly stirring and mixing, adding sodium hydroxide to adjust the pH value of the solution to 9, slowly dropwise adding 90-110 parts of acetone, and preserving heat for 0.5-1.5h after dropwise adding; after the heat preservation is finished, starting to dropwise add 300 parts of formaldehyde II solution, after the dropwise addition is finished, heating to 90-95 ℃, and preserving the heat for 2-4 h; after the heat preservation is finished, cooling to below 70 ℃ for later use, and recording as mother liquor B;

3) according to the use of the compound liquid, the mother liquid A and the mother liquid B are compounded into compound liquids with different proportions.

Further, according to the method for recycling the resorcinol distillation residue, in the step 1), 260 parts of purified water is weighed and placed in a reaction kettle I according to the mass ratio, the mixture is heated to 40 ℃, 180 parts of sulfanilic acid, 85 parts of phenol, 15 parts of urea and 95 parts of resorcinol distillation residue are sequentially added, the mixture is stirred and mixed uniformly, after the mixture is completely dissolved, the mixture is continuously heated to 60 ℃, sodium hydroxide is added to adjust the pH value of the solution to 9, after the mixture is stirred and mixed uniformly, 162 parts of formaldehyde I solution is slowly dripped, and after the dripping is finished, the temperature is raised to 90-95 ℃ and the temperature is kept for 2.5 hours; and after the heat preservation is finished, adding 175 parts of purified water into the reaction kettle I, and cooling to below 70 ℃ for later use to be recorded as mother liquor A.

Further, according to the method for recycling the resorcinol distillation residue, in the step 2), 460 parts of purified water is weighed into the reaction kettle II according to the mass ratio, 136 parts of sulfonating agent and 15-50 parts of resorcinol distillation residue are slowly added while stirring, the mixture is uniformly stirred and mixed, then the mixture is heated to 40 ℃, sodium hydroxide is added to adjust the pH value of the solution to 9, 90-110 parts of acetone is slowly added dropwise, and the temperature is kept for 0.5-1.5 hours after the dropwise addition; after the heat preservation is finished, starting to dropwise add 300 parts of formaldehyde II solution, after the dropwise addition is finished, heating to 90-95 ℃, and preserving the heat for 2-4 h; and after the heat preservation is finished, cooling to below 70 ℃ for later use, and recording as mother liquor B.

Further, according to the method for recycling the resorcinol distillation residue, in the step 3), when the compound liquid is used as a cement water reducing agent, the mother liquid A and the mother liquid B are mixed according to the ratio of 5: 3, compounding; when the compound liquid is used as a coal slurry additive, the mother liquid A and the mother liquid B are mixed according to the ratio of 1: 9, compounding.

Further, according to the method for resource utilization of the resorcinol distillation residues, the dripping time of the formaldehyde I solution is 1.5-3h, the dripping time of the formaldehyde II solution is 1.5-4h, and the temperature in the dripping process is not more than 80 ℃; the formaldehyde I solution and the formaldehyde II solution are 35-37% by mass of formaldehyde solutions.

Further, in the method for recycling the resorcinol distillation residue, the sulfonating agent is at least one of sodium sulfite, sodium bisulfite and sodium metabisulfite.

Further, according to the method for recycling the resorcinol distillation residue, the temperature of the acetone is not more than 55 ℃ in the dropping process, and the dropping time is 20-40 min.

Further, according to the method for recycling the resorcinol distillation residue, the molar ratio of the sulfonating agent to the acetone is 0.3-0.68: 1, the molar ratio of the formaldehyde I solution to the acetone is 1.6-2: 1.

the invention has the beneficial effects that:

1. the invention provides a method for recycling resorcinol distillation residues, which has the advantages of simple and convenient operation, easy control of reaction conditions, simple production process and no discharge of three wastes.

2. The obtained product has better dispersibility to coal water slurry or cement concrete under lower mixing amount, and can obtain various additives suitable for different coal types and cement after compounding, and in addition, the product can be compounded with various other water reducing agents or dispersing agents in any proportion.

3. The water reducing agent can obviously improve the water purifying slurry of the water reducing agent with time, has no loss of the water purifying slurry within 3 hours, and has higher water reducing rate.

4. The release amount of free formaldehyde in the product is low, and the obtained water reducing agent product is safer and more environment-friendly.

Of course, it is not necessary for any one product that embodies the invention to achieve all of the above advantages simultaneously.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.

FIG. 1 is a schematic diagram of the particle size distribution of a coal sample 1 according to the present invention;

FIG. 2 is a schematic diagram of the particle size distribution of coal sample 2 in the present invention.

Detailed Description

According to the relevant regulations of the water reducing agent in GB 8076 plus 2008 concrete admixture, the slump of the concrete mixed with the water reducing agent prepared in the embodiment and the comparative example when the concrete is taken out of the machine, the slump of the concrete after 1h, 2h and 3h are measured, and the slump of the concrete after 20min, 40min and 60min are measured. The test adopts the middle-linked cement, and the mixing amount of the water reducing agent is 0.7 percent (fold-fixed) of the weight of the cement.

The instrument and the detection method for detecting the characteristics of the coal water slurry are as follows:

1. the experimental apparatus is a Brookield Bohler fly DV1 viscometer, a 150ml beaker, and a halogen moisture meter, USA.

2. Experimental procedure

Firstly, a power supply of the experimental instrument is connected, and the level is adjusted and the zero is automatically adjusted. And secondly, putting the same amount of sample in a 150ml beaker to ensure the temperature and the quality of the measured sample. The beaker is placed under the instrument, the rotor is brought into the sample until the scale mark on the rotor, and the start key is pressed to start the test. Measuring the viscosity of the sample by using a 62# rotor at the speed of 20 parts of the shearing speed. The viscosity comparison must be carried out under the same instrument, rotor, speed, vessel, temperature and test time.

The experimental instrument and the detection method used for the fluidity experiment are as follows:

1. laboratory apparatus

a. Truncated cone circular die: the diameter of the upper opening is 36mm, the diameter of the lower opening is 60mm, the height is 60mm, and the inner wall of the metal product is smooth and has no seam;

b. glass plates (400X 400mm, thickness 5 mm);

c. straightedge in steel, (300 mm);

d. and (4) scraping the blade.

2. Experimental procedure

Firstly, the glass plate is placed in a horizontal position, and the surface of the glass plate, the truncated cone round die, the stirrer and the stirring pot are wetted by wet cloth without water stain. And secondly, placing the truncated cone round die in the center of the glass plate and covering the truncated cone round die with wet cloth for later use. Thirdly, the water-coal-slurry is quickly injected into the truncated cone circular mould, the truncated cone circular mould is scraped by a scraper, the water-coal-slurry is lifted vertically to flow on the glass plate until the water-coal-slurry does not flow, the maximum diameters of two mutually vertical directions of the flowing part are measured by a ruler, and the average value is taken as the fluidity (the expansion degree) of the water-coal-slurry.

And (3) stability testing, namely testing the stability by adopting a rod dropping method, wherein the required experimental apparatus and the detection method are as follows:

experimental apparatus, 150ml beaker, electronic balance, preservative film, 300mm ruler, timer.

Experimental procedure 150g of coal water slurry was weighed into a 150ml beaker, completely sealed with a sealing film, left at room temperature, and the depth (H1 and H2) of a 10 × 200mm glass rod was measured at 10s for 5 minutes and the actual depth (H) was measured simultaneously over 24 hours to calculate the soft precipitation rate and the hard precipitation rate according to the following equation. Soft precipitation rate (H-H1)/Hx100%, and hard precipitation rate (H-H2)/Hx100%

The method for detecting the granularity of the coal water slurry comprises the following steps:

1. the experimental instrument is an LS100Q laser particle size analyzer

2. Theory of scattering of light by particles it is well known that light is a cell wave that interacts with particles as they encounter them during propagation, some of which will deviate from the original direction of travel, known as scattering. The working principle of the instrument, namely the laser particle analyzer, comprises a measuring unit, a sample cell, a computer and a printer. The measuring unit is the core of the instrument and is responsible for emission of laser, photoelectric conversion of scattered signals, preprocessing of photoelectric signals and A/D conversion. The circulating sample cell is used for conveying a sample to be measured to a measuring area of the measuring unit. The computer is used for processing the photoelectric signals, converting the energy distribution of scattered light into the particle size distribution of the sample and forming a test report, and the printer is used for outputting a hard copy of the test report, namely printing the test report.

3. Operating procedures

Test unit preheating

The main switch of the instrument power supply is turned on, and the laser power can be stabilized after at least half an hour. If the environmental temperature of the laboratory is low, the preheating time needs to be prolonged properly. (if repeat test, this step can be skipped)

② opening the test software of LS100Q

a, controlling a tab-selecting automatic cleaning (the step can be manually operated on a water bath box); b, setting the rotating speed of the pump: setting the intensity and time of ultrasound if necessary, adding a proper amount of dispersion medium (usually distilled water) into a 20ml beaker; c, turning on a pump (which can also be carried out on a water bath tank) in software, measuring an option card, manually setting, and measuring a display window; d, option bar: selecting test contents in a measurement option window; column for substance e: setting optical characteristics, selecting correct sample substance names and dispersing agent names, and inputting test sample numbers or names; f, calculating the result: selecting model tab-general-determine; g, measurement column: setting pump speed, ultrasonic time and intensity and test content in a measurement tab, and testing a background value before first measurement; and h, clicking the start of the measurement display window, slowly adding the sample by using a disposable dropper, and starting to measure the sample when the laser shading degree is within a set range (8-12%).

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

The invention provides an embodiment of a method for recycling resorcinol distillation residues to synthesize mother liquor A, which specifically comprises the following steps:

weighing 350 parts of purified water according to the mass ratio, heating the water in a reaction kettle I to 40 ℃, sequentially adding 150 parts of sulfanilic acid sodium salt, 90 parts of phenol, 10 parts of urea and 50 parts of resorcinol distillation residue, stirring and mixing uniformly, continuously heating the water to 60 ℃ after complete dissolution, adding sodium hydroxide to adjust the pH value of the solution to 9, stirring and mixing uniformly, beginning to slowly dropwise add 130 parts of formaldehyde I solution, heating the solution to 90-95 ℃ after dropwise addition, and keeping the temperature for 2.5 hours; after the heat preservation is finished, 165 parts of purified water is added into the reaction kettle I, and the temperature is reduced to below 70 ℃ for later use and is recorded as mother liquor A1.

Wherein the resorcinol distillation residue has a solid content of 67% and a pH of 4.

Wherein the mass fraction of the formaldehyde I solution is 35%, the dripping speed of the formaldehyde I solution is slow, the dripping time is controlled to be 2 hours, and the temperature in the dripping process is not more than 80 ℃.

Example 2

The invention provides an embodiment of a method for recycling resorcinol distillation residues to synthesize mother liquor A, which specifically comprises the following steps:

weighing 322 parts of purified water according to the mass ratio, placing the weighed purified water into a reaction kettle I, heating the mixture to 40 ℃, sequentially adding 150 parts of sulfanilic acid sodium salt, 70 parts of phenol, 15 parts of urea and 90 parts of resorcinol distillation residue, stirring and mixing the mixture uniformly, continuing to heat the mixture to 60 ℃ after the mixture is completely dissolved, adding sodium hydroxide to adjust the pH value of the solution to 9, beginning to slowly dropwise add 130 parts of formaldehyde I solution after stirring and mixing the mixture uniformly, heating the solution to 90-95 ℃ after the dropwise addition is finished, and keeping the temperature for 3 hours; after the heat preservation is finished, 165 parts of purified water is added into the reaction kettle I, and the temperature is reduced to below 70 ℃ for later use and is recorded as mother liquor A2.

Wherein the resorcinol distillation residue has a solid content of 67% and a pH of 4.

Wherein the mass fraction of the formaldehyde I solution is 36%, the dripping speed of the formaldehyde I solution is slow, the dripping time is controlled to be 2 hours, and the temperature in the dripping process is not more than 80 ℃.

Example 3

The invention provides an embodiment of a method for recycling resorcinol distillation residues to synthesize mother liquor A, which specifically comprises the following steps:

weighing 305 parts of purified water according to the mass ratio, heating the water in a reaction kettle I to 40 ℃, sequentially adding 150 parts of sulfanilic acid sodium salt, 50 parts of phenol, 20 parts of urea and 120 parts of resorcinol distillation residue, stirring and mixing uniformly, continuously heating the water to 60 ℃ after complete dissolution, adding sodium hydroxide to adjust the pH value of the solution to 9, stirring and mixing uniformly, beginning to slowly dropwise add 130 parts of formaldehyde I solution, heating the solution to 90-95 ℃ after dropwise addition, and keeping the temperature for 3 hours; after the heat preservation is finished, 165 parts of purified water is added into the reaction kettle I, and the temperature is reduced to below 70 ℃ for later use and is recorded as mother liquor A3.

Wherein the solid content of the resorcinol distillation residue is 65% and the pH is 4.

Wherein the mass fraction of the formaldehyde I solution is 37%, the dripping speed of the formaldehyde I solution is slow, the dripping time is controlled to be 1.5h, and the temperature in the dripping process is not more than 80 ℃.

Example 4

The invention provides an embodiment of a method for recycling resorcinol distillation residues to synthesize mother liquor B, which specifically comprises the following steps:

weighing 360 parts of purified water according to the mass ratio, slowly adding 140 parts of sodium sulfite and 20 parts of resorcinol distillation residue while stirring, uniformly stirring and mixing, heating to 40 ℃, adding sodium hydroxide to adjust the pH value of the solution to 9, slowly dropwise adding 96 parts of acetone, and keeping the temperature for 1h after dropwise adding; starting to dropwise add 268 parts of formaldehyde II solution after the heat preservation is finished, heating to 90-95 ℃ after the dropwise addition is finished, and preserving the heat for 3 hours; and after the heat preservation is finished, cooling to below 70 ℃ for later use, and recording as mother liquor B1.

Wherein the solid content of the resorcinol distillation residue is 65% and the pH is 4.

Wherein the mass fraction of the formaldehyde II solution is 36%, the dripping speed of the formaldehyde II solution is slow, the dripping time is controlled to be 1.5h, and the temperature in the dripping process is not more than 80 ℃.

Example 5

The invention provides an embodiment of a method for recycling resorcinol distillation residues to synthesize mother liquor B, which specifically comprises the following steps:

the invention provides an embodiment of a method for recycling resorcinol distillation residues to synthesize mother liquor B, which specifically comprises the following steps:

weighing 300 parts of purified water according to the mass ratio, slowly adding 130 parts of sodium sulfite, 10 parts of sodium styrene sulfonate and 15 parts of resorcinol distillation residue while stirring, uniformly stirring and mixing, heating to 40 ℃, adding sodium hydroxide to adjust the pH value of the solution to 9, slowly dropwise adding 80 parts of acetone, and keeping the temperature for 2 hours after dropwise adding; after the heat preservation is finished, 200 parts of formaldehyde II solution is dripped, and after the dripping is finished, the temperature is raised to 90-95 ℃ and the heat preservation is carried out for 2 hours; and after the heat preservation is finished, cooling to below 70 ℃ for later use, and recording as mother liquor B2.

Wherein the solid content of the resorcinol distillation residue is 65% and the pH is 4.

Wherein the mass fraction of the formaldehyde II solution is 36%, the dripping speed of the formaldehyde II solution is slow, the dripping time is controlled to be 1.5h, and the temperature in the dripping process is not more than 80 ℃.

Example 6

The invention provides an embodiment of a method for recycling resorcinol distillation residues to synthesize mother liquor B, which specifically comprises the following steps:

weighing 420 parts of purified water according to the mass ratio, slowly adding 145 parts of sodium sulfite, 5 parts of sodium styrene sulfonate and 30 parts of resorcinol distillation residue while stirring, uniformly stirring and mixing, heating to 40 ℃, adding sodium hydroxide to adjust the pH value of the solution to 9, slowly dropwise adding 100 parts of acetone, and keeping the temperature for 2 hours after dropwise adding; after the heat preservation is finished, 270 parts of formaldehyde II solution is dripped, and after the dripping is finished, the temperature is raised to 90-95 ℃ and the heat preservation is carried out for 3 hours; and after the heat preservation is finished, cooling to below 70 ℃ for later use, and recording as mother liquor B3.

Wherein the solid content of the resorcinol distillation residue is 65% and the pH is 4.

Wherein the mass fraction of the formaldehyde II solution is 37%, the dripping speed of the formaldehyde II solution is slow, the dripping time is controlled to be 2 hours, and the temperature in the dripping process is not more than 80 ℃.

Example 7

The invention provides an embodiment of a method for recycling resorcinol distillation residues to synthesize mother liquor B, which specifically comprises the following steps:

weighing 480 parts of purified water according to the mass ratio, slowly adding 150 parts of sodium sulfite, 10 parts of sodium styrene sulfonate and 30 parts of resorcinol distillation residue while stirring, uniformly stirring and mixing, heating to 40 ℃, adding sodium hydroxide to adjust the pH value of the solution to 9, slowly dropwise adding 110 parts of acetone, and preserving heat for 2 hours after dropwise adding; after the heat preservation is finished, 280 parts of formaldehyde II solution is dripped, and after the dripping is finished, the temperature is raised to 90-95 ℃ and the heat preservation is carried out for 3 hours; and after the heat preservation is finished, cooling to below 70 ℃ for later use, and recording as mother liquor B4.

Wherein the solid content of the resorcinol distillation residue is 65% and the pH is 4.

Wherein the mass fraction of the formaldehyde II solution is 35%, the dripping speed of the formaldehyde II solution is slow, the dripping time is controlled to be 2 hours, and the temperature in the dripping process is not more than 80 ℃.

Example 8

The invention provides an embodiment of a method for recycling resorcinol distillation residues to synthesize mother liquor B, which specifically comprises the following steps:

weighing 500 parts of purified water according to the mass ratio, slowly adding 140 parts of sodium sulfite, 15 parts of sodium styrene sulfonate and 30 parts of resorcinol distillation residue while stirring, uniformly stirring and mixing, heating to 40 ℃, adding sodium hydroxide to adjust the pH value of the solution to 9, slowly dropwise adding 120 parts of acetone, and preserving heat for 2 hours after dropwise adding; after the heat preservation is finished, 300 parts of formaldehyde II solution is dripped, and after the dripping is finished, the temperature is raised to 90-95 ℃ and the heat preservation is carried out for 4 hours; and after the heat preservation is finished, cooling to below 70 ℃ for later use, and recording as mother liquor B5.

Wherein the solid content of the resorcinol distillation residue is 65% and the pH is 4.

Wherein the mass fraction of the formaldehyde II solution is 36%, the dripping speed of the formaldehyde II solution is slow, the dripping time is controlled to be 2 hours, and the temperature in the dripping process is not more than 80 ℃.

Comparative example 1

The invention provides a comparative example of a method for resource utilization of resorcinol distillation residues, which specifically comprises the following steps:

weighing 395 parts of purified water according to the mass ratio, heating the purified water to 40 ℃, sequentially adding 150 parts of sodium sulfanilate, 70 parts of phenol and 15 parts of urea, uniformly stirring and mixing, continuously heating the mixture to 60 ℃ after complete dissolution, adding sodium hydroxide to adjust the pH value of the solution to 9, slowly dropwise adding 130 parts of formaldehyde I solution after uniform stirring and mixing, heating the solution to 90-95 ℃ after dropwise adding, and keeping the temperature for 3 hours; after the heat preservation is finished, 165 parts of purified water is added into the reaction kettle I, and the temperature is reduced to below 70 ℃ to be used as blank comparison of the mother solution A.

Wherein the mass fraction of the formaldehyde I solution is 37%, the dripping speed of the formaldehyde I solution is slow, the dripping time is controlled to be 1.5h, and the temperature in the dripping process is not more than 80 ℃.

Comparative example 2

The invention provides a comparative example of a method for resource utilization of resorcinol distillation residues, which specifically comprises the following steps:

weighing 360 parts of purified water according to the mass ratio, adding 140 parts of sodium sulfite slowly while stirring, heating to 40 ℃ after uniformly stirring and mixing, adding sodium hydroxide to adjust the pH of the solution to 9, slowly dropwise adding 96 parts of acetone, and preserving heat for 1h after dropwise adding; starting to dropwise add 268 parts of formaldehyde II solution after the heat preservation is finished, heating to 90-95 ℃ after the dropwise addition is finished, and preserving the heat for 3 hours; and (5) cooling to below 70 ℃ after the heat preservation is finished, and taking the temperature as blank comparison of the mother solution B.

Wherein the mass fraction of the formaldehyde II solution is 36%, the dripping speed of the formaldehyde II solution is slow, the dripping time is controlled to be 1.5h, and the temperature in the dripping process is not more than 80 ℃.

According to the relevant specifications of the water reducing agent in GB 8076 + 2008 concrete admixture, the initial net slurry, 1h net slurry, 2h net slurry, slump at the time of machine exit and slump at the time of 20min (T20), 40min (T40), 60min (T60) of the concrete doped with the water reducing agent prepared in the examples and the comparative examples of the present invention were measured, and the workability comparison of the concrete was observed. The test adopts the middle-linked cement, and the mixing amount of the water reducing agent is 0.7 percent (fold-fixed) of the weight of the cement.

The test results are shown in table 1 below:

TABLE 1

From table 1, it can be seen that the water reducing agents a1, a2, A3, B1, B2, B3 and B4 obtained in the examples of the present invention can improve the net paste and slump and reduce the loss of net paste and slump and also improve the workability of concrete, as compared with the conventional sulfamic acid-based water reducing agent (comparative example 1) and aliphatic water reducing agent (comparative example 2).

The two kinds of coal samples selected in this example are respectively coal sample 1-Binxian coal and coal sample 2-Gomphrena coal, wherein FIG. 1 is the particle size distribution of coal sample 1, and FIG. 2 is the particle size distribution of coal sample 2.

The coal quality characteristics and some experimental results of the analysis of each group of samples and some compounded samples are shown in the following tables 2 and 3:

TABLE 2

TABLE 3

From tables 2-3, it is known that the resorcinol distillation residue resource utilization synthesis mother liquor A, B is used as a coal water slurry dispersing agent, and particularly, the dispersing agent is prepared after the A and B are compounded, so that the dispersing effect of the resorcinol distillation residue resource utilization synthesis mother liquor can be improved, the viscosity of the coal water slurry is reduced, the fluidity of the coal water slurry is improved, the coal water slurry has a relatively obvious concentration effect, and the stability of the coal water slurry is slightly improved. If the lignin is compounded with the coal water slurry dispersant, the effect is better, and the method is worthy of popularization.

The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.