CN115504702B - Organic acid-protein composite gypsum retarder and preparation method thereof - Google Patents
Organic acid-protein composite gypsum retarder and preparation method thereof Download PDFInfo
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- 239000010440 gypsum Substances 0.000 title claims abstract description 67
- 229910052602 gypsum Inorganic materials 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 102000004169 proteins and genes Human genes 0.000 claims abstract description 57
- 108090000623 proteins and genes Proteins 0.000 claims abstract description 57
- 239000002699 waste material Substances 0.000 claims abstract description 28
- 150000007524 organic acids Chemical class 0.000 claims abstract description 20
- 239000010985 leather Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000007062 hydrolysis Effects 0.000 claims abstract description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 8
- 238000001694 spray drying Methods 0.000 claims abstract description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 16
- 235000015165 citric acid Nutrition 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 238000000889 atomisation Methods 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- 230000000979 retarding effect Effects 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 239000000843 powder Substances 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 235000018102 proteins Nutrition 0.000 description 48
- 238000010276 construction Methods 0.000 description 17
- 239000000463 material Substances 0.000 description 9
- 239000007921 spray Substances 0.000 description 7
- 238000011160 research Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000011265 semifinished product Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229930182555 Penicillin Natural products 0.000 description 1
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 235000006468 Thea sinensis Nutrition 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 206010003549 asthenia Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000020279 black tea Nutrition 0.000 description 1
- 239000002639 bone cement Substances 0.000 description 1
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 description 1
- 239000001354 calcium citrate Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 235000021190 leftovers Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 229940049954 penicillin Drugs 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 235000004252 protein component Nutrition 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000013337 tricalcium citrate Nutrition 0.000 description 1
Classifications
-
- 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
- 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
- C04B2103/20—Retarders
- C04B2103/22—Set retarders
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an organic acid-protein composite gypsum retarder and a preparation method thereof. The organic acid-protein composite gypsum retarder takes waste leather protein as a raw material, organic acid is introduced to regulate the molecular weight of the protein through hydrolysis, and meanwhile, the organic acid is also used as an effective retarding component to form the organic acid-protein composite gypsum retarder. The invention firstly mixes the organic acid solution and the waste leather protein powder according to a certain proportion, hydrolyzes the protein under the acid condition to a molecular weight range with high retarding efficiency, and then removes the water in the mixture by spray drying to prepare the organic acid-protein composite gypsum retarder. The gypsum composite retarder has the advantages of simple preparation process, low energy consumption, low cost, no pollution, capability of fully playing the synergistic effect of organic acid and protein, good solubility, high stability, no special smell, good retarding effect on gypsum, small strength loss and the like, and is suitable for industrial mass production.
Description
Technical Field
The invention discloses an organic acid-protein composite gypsum retarder and a preparation method thereof, and relates to the technical field of gypsum retarders.
Background
Gypsum is widely used in the construction industry as an excellent cementing material, and is one of three inorganic cementing materials. Compared with other cementing materials, the gypsum has the advantages of low energy consumption, light weight, good heat preservation and insulation performance, strong processability and plasticity, and cyclic utilization, and belongs to green cementing materials. Through a certain production process, gypsum can be processed into various gypsum variant materials with different types and properties. Such as construction gypsum, can be used to produce plasters, renders, ceilings, decorative acoustical panels, and other decorative components.
Because the early strength of the building gypsum material develops faster, the setting and hardening time is short, the fluidity can be lost within a few minutes, and the normal construction requirement is difficult to meet. To solve this problem, setting time is usually adjusted by adding retarder, so that the building gypsum slurry can maintain plasticity for a long time to improve workability. The common building gypsum retarder mainly comprises organic acid and salts thereof, alkaline phosphate, protein retarder, composite retarder and the like. In the past, researches show that organic acids such as citric acid, malic acid, succinic acid, adipic acid, tartaric acid, sodium tartrate, salicylic acid and the like have a certain retarding effect on gypsum by alkaline phosphates such as sodium tripolyphosphate and the like, and meanwhile, the strength loss of the gypsum is large. The organic acid citric acid has the strongest retarding effect on gypsum, and has obvious retarding effect when the mixing amount is smaller, but has larger strength loss on gypsum materials.
The protein retarder has the characteristics of good retarding effect and small strength loss to gypsum, so that the protein retarder becomes a hot spot in the research field of gypsum retarders. Commonly used protein retarders include natural proteins and hydrolysis or decomposition products of proteins, and the like. Related researches show that natural proteins such as bone glue, black tea powder and the like can be added into gypsum materials as gypsum retarder, so that the setting time of gypsum is prolonged, and the workability is improved. Many researches show that the method can be used for producing protein retarders by processing the waste proteins, so that the production cost is greatly reduced while the reutilization of the waste proteins is realized. For example, the protein gypsum retarder can be prepared by processing wastes with main components of protein such as wheat protein, penicillin mycelium, leather leftovers and gelatin. The molecular weight of the polypeptide in the protein retarder plays a leading role in retarding effect of the retarder, and protein wastes are often required to be processed in the production process. At present, the processing modes of protein waste comprise hydrolysis and enzyme methods. The hydrolysis method generally hydrolyzes proteins through inorganic acid such as hydrochloric acid or sulfuric acid, strong alkali such as calcium hydroxide or sodium hydroxide and other catalysts, adjusts the molecular weight of the proteins to a proper range, and removes acid and alkali or removes salt formed by neutralization to obtain the protein retarder. The protein retarder is prepared by treating the waste proteins with specific protease in an enzymatic method, but the method is often accompanied by higher production cost and harsh production environment.
In recent years, due to the need for industrial production, various composite gypsum-based retarders have been developed and used. Because the protein retarder has less influence on the gypsum strength, a certain amount of protein component is often added in the production of the composite gypsum retarder. If the composite gypsum retarder contains protein, the molecular weight of the composite gypsum retarder is often important. The molecular weight of the protein is regulated as the first step, the impurity component is removed to obtain a semi-finished product, and the semi-finished product is synthesized with other substances or is simply mixed according to a certain proportion to prepare the composite gypsum retarder by a two-step method. Complicated process, complex technology and high energy consumption, wherein the removal of salt or catalyst generated by regulating the molecular weight of protein is often accompanied by higher production cost. Therefore, the preparation method for developing the composite retarder with one step, low cost, simple process, good retarding effect and small strength loss is unprecedented.
Disclosure of Invention
The invention mainly solves the technical problem of overcoming the defects of the background technology and provides the organic acid-protein composite gypsum retarder prepared by one step and the preparation method thereof. The composite gypsum retarder takes waste leather protein as a raw material, the molecular weight of the protein is regulated and controlled by introducing organic acid to hydrolyze the waste protein under an acidic condition, and meanwhile, the organic acid is also used as an effective retarder component, so that the organic acid-protein composite gypsum retarder is prepared by one step. The organic acid and the protein in the composite retarder have synergistic effect, so that the retarder has a stronger retarding effect and has smaller strength loss on gypsum materials; meanwhile, the preparation method has the advantages of simple process, low energy consumption and low production cost by one-step preparation.
An organic acid-protein composite gypsum retarder and a preparation method thereof are provided, wherein the composite gypsum retarder is composed of organic acid and hydrolyzed waste protein thereof.
An organic acid-protein composite gypsum retarder and a preparation method thereof, wherein the organic acid-protein composite gypsum retarder is prepared by one-step hydrolysis and comprises the following steps:
(1) The weight portions are as follows: fully mixing 5-9 parts of waste leather protein, 1-5 parts of organic acid and 50-90 parts of water in a reaction kettle, and dissolving;
(2) Heating at 80-100 ℃ to hydrolyze the mixed solution for 12-24 h, and spray drying the hydrolyzed solution after the hydrolysis is completed to obtain the organic acid-protein gypsum retarder powder.
Preferably, the organic acid includes one or two of citric acid, oxalic acid, succinic acid, malic acid, tartaric acid, and the like.
Preferably, the waste leather proteins are chromium-depleted proteins and have an average molecular weight of 10w to 15w Da.
Preferably, the atomization temperature of the spray drying of the hydrolysate is 150-200 DEG C
The invention has the positive beneficial effects that
The invention processes the organic acid and the waste leather protein by a hydrothermal method, utilizes the organic acid to regulate and control the molecular weight of the waste leather protein, and simultaneously uses the organic acid as an effective retarder component to prepare the organic acid-protein composite gypsum retarder by one step. The organic acid and the protein play a role in synergistic retarding, have a certain role in antioxidation and sterilization, and can improve the stability of the composite retarder. And spray drying the hydrolyzed mixed solution by a spray drying method to improve the solubility of the retarder. Citric acid is a flavoring agent, and no other odor regulator is added in the process. Compared with the prior two-step method for producing the composite gypsum retarder, the method has the advantages of simple process, low energy consumption, low cost, no pollution, good solubility, high stability, no special smell, good retarder effect on gypsum, small strength loss and the like. Meanwhile, the invention also provides a feasible technical route for recycling the waste protein resources.
Detailed Description
The present invention will be described in detail with reference to the following examples, but is not limited to the scope of the present invention:
example 1
Uniformly mixing one part of citric acid, ten parts of waste leather protein and one hundred parts of water, adding the mixture into a reaction kettle, and reacting for 12-24 hours at 80-100 ℃. The solution was prepared into retarder powder by means of a spray dryer and then added to the construction gypsum and the setting time and mechanical properties of the construction gypsum were determined according to GB/T17669.4-1999 and GB/T17669.3-1999, respectively.
Example two
Uniformly mixing one part of citric acid, four parts of waste leather proteins and forty parts of water, adding the mixture into a reaction kettle, and reacting for 12-24 hours at 80-100 ℃. The solution was prepared into retarder powder by means of a spray dryer and then added to the construction gypsum and the setting time and mechanical properties of the construction gypsum were determined according to GB/T17669.4-1999 and GB/T17669.3-1999, respectively.
Example III
Uniformly mixing one part of citric acid, one part of waste leather protein and ten parts of water, adding the mixture into a reaction kettle, and reacting for 12-24 hours at 80-100 ℃. The solution was prepared into retarder powder by means of a spray dryer and then added to the construction gypsum and the setting time and mechanical properties of the construction gypsum were determined according to GB/T17669.4-1999 and GB/T17669.3-1999, respectively.
Example IV
Mixing one part of oxalic acid, four parts of waste leather proteins and fifty parts of water uniformly, adding the mixture into a reaction kettle, and reacting for 12-24 hours at 80-100 ℃. The solution was prepared into retarder powder by means of a spray dryer and then added to the construction gypsum and the setting time and mechanical properties of the construction gypsum were determined according to GB/T17669.4-1999 and GB/T17669.3-1999, respectively.
Example five
Uniformly mixing one part of succinic acid, five parts of waste leather proteins and one hundred parts of water, adding the mixture into a reaction kettle, and reacting for 12-24 hours at 80-100 ℃. The solution was prepared into retarder powder by means of a spray dryer and then added to the construction gypsum and the setting time and mechanical properties of the construction gypsum were determined according to GB/T17669.4-1999 and GB/T17669.3-1999, respectively.
Example six
Uniformly mixing one part of tartaric acid, ten parts of waste leather proteins and forty parts of water, adding the mixture into a reaction kettle, and reacting for 12-24 hours at 80-100 ℃. The solution was prepared into retarder powder by means of a spray dryer and then added to the construction gypsum and the setting time and mechanical properties of the construction gypsum were determined according to GB/T17669.4-1999 and GB/T17669.3-1999, respectively.
Table 1 the composite retarder prepared in each example was incorporated into construction gypsum (0.05% incorporated, blank: pure gypsum) and the setting time and strength (3 d wet strength) test results of construction gypsum were compared:
| initial setting time/min | Final setting time/min | Flexural Strength/MPa | Compressive Strength/MPa | |
| Blank space | 28 | 37 | 2.4 | 3.5 |
| Example 1 | 89 | 100 | 2.4 | 3.5 |
| Example two | 107 | 119 | 2.4 | 3.5 |
| Example III | 154 | 166 | 1.7 | 2.5 |
| Example IV | 95 | 103 | 2.1 | 3.0 |
| Example five | 70 | 85 | 2.2 | 3.3 |
| Example six | 78 | 90 | 2.3 | 3.2 |
Table 2 citric acid, compound retarder, hydrolyzed waste protein (preparation method and conditions are the same as the compound retarder, citric acid is removed after hydrolysis) were incorporated into building gypsum (incorporation amount 0.15%), setting time of building gypsum and compression strength detection result were compared:
under the condition that the mixing amount of the retarder is the same, compared with citric acid and waste protein, the composite retarder has better retarding effect and small strength loss.
Determination of molecular weight
And (3) dissolving the retarder prepared in the second embodiment in water, adding a certain amount of calcium hydroxide, and reacting citric acid with the calcium hydroxide to generate calcium citrate precipitate to remove the citric acid. After filtration, the remaining solution is spray dried to give a protein powder of suitable molecular weight. The average molecular weight of the waste leather proteins and the hydrolyzed proteins obtained after separation of citric acid in the examples were determined by Gel Permeation Chromatography (GPC) and were 10w to 15w Da and 8w Da, respectively
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (4)
1. An organic acid-protein composite gypsum retarder and a preparation method thereof are characterized in that the composite gypsum retarder consists of organic acid and hydrolyzed waste protein thereof; the organic acid-protein composite gypsum retarder is prepared by one-step hydrolysis and comprises the following steps:
(1) Fully mixing and dissolving 5-9 parts by weight of waste leather protein, 1-5 parts by weight of organic acid and 50-90 parts by weight of water in a reaction kettle;
(2) Hydrolyzing the mixed solution at 80-100 ℃ for 12-24 hours, and then spray drying the hydrolyzed solution to obtain the powdery organic acid-protein gypsum retarder.
2. The method according to claim 1, wherein the organic acid in the step (1) comprises one or two of citric acid, oxalic acid, succinic acid, malic acid and tartaric acid.
3. The method according to claim 1, wherein the waste leather proteins of step (1) are chromium-removed proteins and have an average molecular weight of 10w to 15w Da.
4. The method according to claim 1, wherein the spray-drying of the hydrolyzed solution in step (2) is carried out at an atomization temperature of 150 to 200 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211355668.9A CN115504702B (en) | 2022-11-01 | 2022-11-01 | Organic acid-protein composite gypsum retarder and preparation method thereof |
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| CN202211355668.9A CN115504702B (en) | 2022-11-01 | 2022-11-01 | Organic acid-protein composite gypsum retarder and preparation method thereof |
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| CN115504702A CN115504702A (en) | 2022-12-23 |
| CN115504702B true CN115504702B (en) | 2023-07-28 |
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