CN105906228A - Method for preparation of cement grinding aid additive from glycerin rectification residue - Google Patents

Method for preparation of cement grinding aid additive from glycerin rectification residue Download PDF

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Publication number
CN105906228A
CN105906228A CN201610232446.6A CN201610232446A CN105906228A CN 105906228 A CN105906228 A CN 105906228A CN 201610232446 A CN201610232446 A CN 201610232446A CN 105906228 A CN105906228 A CN 105906228A
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CN
China
Prior art keywords
rectification residue
glycerol
water
raw material
glycerin
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Pending
Application number
CN201610232446.6A
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Chinese (zh)
Inventor
陈登龙
王珊珊
李敏
黄秀萍
刘金玲
王勇
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Quangang Petrochemical Research Institute of Fujian Normal University
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Quangang Petrochemical Research Institute of Fujian Normal University
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Priority to CN201610232446.6A priority Critical patent/CN105906228A/en
Publication of CN105906228A publication Critical patent/CN105906228A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/52—Grinding aids; Additives added during grinding

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Polyethers (AREA)

Abstract

The invention discloses a method for preparation of a cement grinding aid additive from glycerin rectification residue. The method is characterized by including the steps of: (1) adding a certain amount of sodium tripolyphosphate into the glycerin rectification residue, stirring the substances evenly, then adding lye to adjust the pH to 9-11; (2) subjecting the step (1) treated glycerin rectification residue to reduced pressure distillation to remove water; (2) adding ethylene glycol into the glycerin rectification residue treated in step (2), conducting stirring and standing, then performing filtering to remove salt; (4) adding a certain amount of water into the glycerin rectification residue treated in step (3), stirring the substances evenly, then adding an acidic solution to adjust the pH to neutral; and (5) adding a certain amount of activated carbon into the glycerin rectification residue treated in step (4) to conduct color removal, and performing filtering to obtain a mixed solution of polyglycerol, ethylene glycol and water. The mixed solution prepared by the method can be used as a cement grinding aid additive.

Description

A kind of method preparing cement agent addition agent for raw material with glycerol rectification residue
Technical field
The invention belongs to comprehensive utilization of resources field, be specifically related to a kind of method preparing cement agent addition agent for raw material with glycerol rectification residue.
Background technology
Cement pulverizing course use grinding aid has been the common practice of current cement production enterprise.In order to reduce energy consumption, improving mill efficiency, the use of grinding aid can be that cement production enterprise brings obvious economic benefit.The Main Function adding grinding aid is to reduce or terminate cement granules agglomeration in grinding process, improve cement fineness and specific surface area, or grinding is under equal fineness, add grinding aid to significantly improve the efficiency of grinding, reduction grinding energy.Meanwhile, grinding aid spontaneously can adsorb on trickle material particles surface, beneficially the reduction of surface energy, thus cement performance after improving grinding.
At present, domestic and international application widest cement grinding aid major part prepares with the single or compounding of the industrial chemical products such as amine, polyalcohols, alcamines, lignin sulfonate, fatty acid and salt, alkyl sulfonic acid class, preferably meet the requirement of powder-grinding process, but along with rising steadily of industrial chemicals price and freight, the price of liquid grinding aid mother solution has risen to about ten thousand yuan at present, and manufacture of cement cost improves the most therewith.Therefore, find a kind of grinding aid tool with low cost, that grinding aid efficiency is high to be of great significance.
Glycerol rectification residue is residue produced during rectification under vacuum technique is become high-purity glycerol by refining crude glycerin, accounts for 1 %～5 % of rectification glycerol total amount.Rectification residue is pitchy thick semi-fluid dynamic liquid, it is mainly composed of polyglycerol and inorganic salt, contain glycerol, soap, protein, jelly and the pigment etc. of a small amount of residual simultaneously, polyglycerol in glycerol rectification residue belongs to polyalcohols, there is stronger surface activity, can be as the additive of cement grinding aid.Additionally, polyglycerol is also excellent cracking resistance economization agent and the plasticizer of cement concrete, advantageously reduce the cracking of concrete material.Therefore, it can reclaim the polyglycerol in glycerol rectification residue, as the raw material of cement grinding aid, there is higher comprehensive reutilization and be worth.
The Impurity removal of the residue after crude glycerine rectification and decolouring are all relatively difficult, and the most treated can not get effectively utilizes polyglycerol therein, thus does not have any commercial value.Glycerol distilled residue reclaims the main method of polyglycerol at present is with solvent (isopropanol, ethylene glycol, aldehydes or ketones etc.) extraction, then carries out decolorizing and refining with activated carbon etc. and forms.See document: Wei Daijun, Li Qingming, " recycling of glycerol distilled residue ", daily chemical industry, 1997.4；Thank to sturdy pines, " glycerol ", light industry publishing house, 1984.But said method there is solvent recovery, solvent consume, solvent contamination, solvent management and reclaim after reprocessing, the problems such as re-refine.Patent 201210576958.6 " cement grinding aid that a kind of chemical spent material is compounding " discloses the cement grinding aid that a kind of chemical spent material is compounding, and it is formed by the mixing of triethanolamine rectification tower bottoms, glycerol distillation heels, calcium lignosulfonate, blackstrap, triethanolamine and water is compounding.Patent 201010230148.6 " cement grinding aid " discloses a kind of cement grinding aid, and this grinding aid is formed by calcium formate solution, compound glycerin bottoms solution, triethanolamine, glycol and molasses are compounding.In the method for above-mentioned application, glycerol distilled residue is all undressed, and reinforcing bar can be caused corrosion by chloride ion therein, affects the endurance quality of cement concrete.Large-scale promotion application is will be unable in the cast of actual cement concrete.
Summary of the invention
The present invention is directed to the reprocessing after solvent recovery during at present big poly-glycerine rectification residue processes, solvent consume, solvent contamination, solvent management and recovery, the problems such as re-refine, with ethylene glycol for desalination solvent, solve chloride ion and cross the etching problem of multipair reinforcing bar, and directly ethylene glycol is applied directly in cement grinding aid, improve the performance of cement grinding aid.
What technical scheme was taked specifically comprises the following steps that
Step 1, adds the Na of certain mass in glycerol rectification residue5P3O10, it is stirring evenly and then adding into alkali liquor regulation pH to 9～11；
Step 2, the glycerol rectification residue after step 1 being processed carries out decompression distillation except water；
Step 3, adds the ethylene glycol of certain mass through step 2 in the glycerol rectification residue after processing, after being sufficiently stirred for, stand certain time, filter desalination；
Step 4, adds a certain amount of water in the glycerol rectification residue after processing through step 3, is stirring evenly and then adding into acid solution regulation pH to neutral；
Step 5, adds a certain amount of activated carbon in the glycerol rectification residue after processing through step 4, stirs a period of time at a certain temperature, filtered while hot, obtain the mixed solution of polyglycerol, ethylene glycol, water after cooling.
Present invention step 1 adds Na5P3O10Quality be 0.1 %～1.0 %；Alkali liquor used is NaOH or Na2CO3, the concentration range of NaOH is 30 %～50 %, Na2CO3Concentration range be 20 %～30 %.
In present invention step 2, decompression is distilled except the technological parameter of water is: heating oil bath temperature is 80～120 DEG C；Condensate temperature is 5～30 DEG C；Stir speed (S.S.) is 50～500 rpm；Vacuum is 0.02～0.095 MPa；Decompression is 0.5～3 h except the water time.
The quality adding ethylene glycol in present invention step 3 is 50 %～200 %；Time of repose is 1～48 h.
The quality adding water in present invention step 4 is 20 %～100 %；Acid solution used is H2SO4Or CH3COOH, the concentration range of acid solution is 10 %～99 %.
The quality adding activated carbon in present invention step 5 is 1 %～5 %；Temperature controls at 60 DEG C～80 DEG C；Mixing time is 5～30 min.
The invention have the advantage that
1. the present invention prepares the additive of cement grinding aid with glycerol rectification residue for raw material, takes full advantage of chemical spent material, turns waste into wealth, decreases environmental pollution.
2. the present invention is with ethylene glycol for desalination solvent, solves chloride ion and crosses the etching problem of multipair reinforcing bar, and be directly applied in cement grinding aid by ethylene glycol, improves the performance of cement grinding aid.
3. the process equipment of the present invention is simple, it is easy to large-scale production.
Detailed description of the invention
The following is several specific embodiments of the present invention, further illustrate the present invention, but the present invention is not limited only to this.
Embodiment 1:
10 Kg glycerol rectification residue adds 50 g Na5P3O10, with 25 % Na2CO3Solution regulation pH to 10, at heating oil bath temperature 100 DEG C, condensate temperature 25 DEG C, vacuum 0.08 MPa, decompression distillation 2 h under conditions of stir speed (S.S.) 300 rpm.After decompression distillation terminates, add 8 kg ethylene glycol, stir, filter after standing 24 h.3 kg water are added, with 10 % H after stirring in filtrate2SO4Regulation pH, to neutral, be subsequently adding 200 g activated carbons, be heated to 70 DEG C, and keep 10 min, and filtered while hot i.e. obtains product after cooling.
Embodiment 2:
10 Kg glycerol rectification residue adds 60 g Na5P3O10, with 30 % Na2CO3Solution regulation pH to 9, at heating oil bath temperature 110 DEG C, condensate temperature 20 DEG C, vacuum 0.08 MPa, decompression distillation 1.5 h under conditions of stir speed (S.S.) 300 rpm.After decompression distillation terminates, add 7.5 kg ethylene glycol, stir, filter after standing 24 h.4 kg water are added, with 10 % H after stirring in filtrate2SO4Regulation pH, to neutral, be subsequently adding 250 g activated carbons, be heated to 80 DEG C, and keep 15 min, and filtered while hot i.e. obtains product after cooling.
Embodiment 3:
10 kg glycerol rectification residues add 50 g Na5P3O10, with 30 % NaOH solution regulation pH to 10, at heating oil bath temperature 110 DEG C, condensate temperature 20 DEG C, vacuum 0.08 MPa, decompression distillation 3 h under conditions of stir speed (S.S.) 350 rpm.After decompression distillation terminates, add 9 kg ethylene glycol, stir, filter after standing 48 h.4 kg water are added, with 30 % CH after stirring in filtrate3COOH regulation pH, to neutral, be subsequently adding 200 g activated carbons, be heated to 70 DEG C, and keep 20 min, and filtered while hot i.e. obtains product after cooling.

Claims (7)

1. the method preparing cement agent addition agent for raw material with glycerol rectification residue, it is characterised in that:
Step 1, adds the Na of certain mass in glycerol rectification residue5P3O10, it is stirring evenly and then adding into alkali liquor regulation pH to 9～11；
Step 2, the glycerol rectification residue after step 1 being processed carries out decompression distillation except water；
Step 3, adds the ethylene glycol of certain mass through step 2 in the glycerol rectification residue after processing, after being sufficiently stirred for, stand certain time, filter desalination；
Step 4, adds the water of certain mass through step 3 in the glycerol rectification residue after processing, be stirring evenly and then adding into acid solution regulation pH to neutral；
Step 5, adds the activated carbon of certain mass, stirs a period of time at a certain temperature, filtered while hot, obtain the mixed solution of polyglycerol, ethylene glycol, water after cooling in the glycerol rectification residue after processing through step 4.
A kind of method preparing cement agent addition agent for raw material with glycerol rectification residue the most according to claim 1, it is characterised in that add Na in step 15P3O10Quality be 0.1 %～1.0 %；Alkali liquor used is NaOH or Na2CO3, the concentration range of NaOH is 30 %～50 %, Na2CO3Concentration range be 20 %～30 %.
A kind of method preparing cement agent addition agent for raw material with glycerol rectification residue the most according to claim 1, it is characterised in that in step 2, decompression is distilled except the technological parameter of water is: heating oil bath temperature is 80～120 DEG C；Condensate temperature is 5～30 DEG C；Stir speed (S.S.) is 50～500 rpm；Vacuum is 0.02～0.095 MPa；Decompression is 0.5～3 h except the water time.
A kind of method preparing cement agent addition agent for raw material with glycerol rectification residue the most according to claim 1, it is characterised in that the quality adding ethylene glycol in step 3 is 50 %～200 %；The time stood is 1～48 h.
A kind of method preparing cement agent addition agent for raw material with glycerol rectification residue the most according to claim 1, it is characterised in that the quality adding water in step 4 is 20 %～100 %；Acid solution used is H2SO4Or CH3COOH, the concentration range of acid solution is 10 %～99 %.
A kind of method preparing cement agent addition agent for raw material with glycerol rectification residue the most according to claim 1, it is characterised in that the quality adding activated carbon in step 5 is 1 %～5 %；Temperature controls at 60 DEG C～80 DEG C；Mixing time is 5～30 min.
A kind of method preparing cement agent addition agent for raw material with glycerol rectification residue the most according to claim 1, it is characterised in that described polyglycerol, ethylene glycol, the mixed solution of water use as cement agent addition agent.
CN201610232446.6A 2016-04-14 2016-04-14 Method for preparation of cement grinding aid additive from glycerin rectification residue Pending CN105906228A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111943552A (en) * 2020-08-14 2020-11-17 徐州吉兴新材料有限公司 Method for producing grinding aid by using heavy alcohol rectification polymerization polyol
CN112174570A (en) * 2020-10-10 2021-01-05 江苏润天建材有限公司 Environment-friendly cement grinding aid and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB663672A (en) * 1949-06-14 1951-12-27 Wolf Ltd Victor New or improved process for the recovery of polyglycerols from distillation residues
CN101898878A (en) * 2010-07-19 2010-12-01 宜兴市宏伟科技有限公司 Cement grinding aid
CN102976659A (en) * 2012-12-27 2013-03-20 广东石油化工学院 Chemical-waste compounded cement grinding aid
CN103524066A (en) * 2013-10-21 2014-01-22 江苏聚威新材料有限公司 Glycerin distillation residue treatment method
CN104817288A (en) * 2015-04-17 2015-08-05 临沂大学 Cement grinding aid composition by taking glycerinum distillation residues as main raw material as well as preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB663672A (en) * 1949-06-14 1951-12-27 Wolf Ltd Victor New or improved process for the recovery of polyglycerols from distillation residues
CN101898878A (en) * 2010-07-19 2010-12-01 宜兴市宏伟科技有限公司 Cement grinding aid
CN102976659A (en) * 2012-12-27 2013-03-20 广东石油化工学院 Chemical-waste compounded cement grinding aid
CN103524066A (en) * 2013-10-21 2014-01-22 江苏聚威新材料有限公司 Glycerin distillation residue treatment method
CN104817288A (en) * 2015-04-17 2015-08-05 临沂大学 Cement grinding aid composition by taking glycerinum distillation residues as main raw material as well as preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
李金惠等: "《危险废物处理技术》", 31 October 2006 *
魏代军等: "《甘油蒸馏残渣的回收利用》", 《表面活性剂工业》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111943552A (en) * 2020-08-14 2020-11-17 徐州吉兴新材料有限公司 Method for producing grinding aid by using heavy alcohol rectification polymerization polyol
CN112174570A (en) * 2020-10-10 2021-01-05 江苏润天建材有限公司 Environment-friendly cement grinding aid and preparation method thereof
CN112174570B (en) * 2020-10-10 2022-05-03 江苏润天建材有限公司 Environment-friendly cement grinding aid and preparation method thereof

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Application publication date: 20160831