CN1062534C - Efficient concrete water-reducing agent - Google Patents
Efficient concrete water-reducing agent Download PDFInfo
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- CN1062534C CN1062534C CN96106515A CN96106515A CN1062534C CN 1062534 C CN1062534 C CN 1062534C CN 96106515 A CN96106515 A CN 96106515A CN 96106515 A CN96106515 A CN 96106515A CN 1062534 C CN1062534 C CN 1062534C
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- Prior art keywords
- reducing agent
- product
- oil
- acid sludge
- add
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Classifications
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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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/36—Bituminous materials, e.g. tar, pitch
-
- 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
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
Abstract
The present invention relates to a high-efficiency water reducing agent for concrete, which has the technical scheme that petroleum hydrocarbons distillate oil of which the aromatic content is larger than 50% is used as a raw material which directly reacts with concentrated sulphuric acid, acid sludge is hydrolyzed and condensed by formaldehyde to be manufactured into the mixed aromatic hydrocarbon sulphonate formaldehyde condensation product high-efficiency water reducing agent in a mixed aromatic hydrocarbon sulphonate formaldehyde condensation product type, and a separated oil product can be neutralized and distilled to obtain qualified light diesel oil. The water reducing agent of the present invention has the advantages of facile raw materials, low price, good quality and simple preparation technology; furthermore, the qualified light diesel oil can be simultaneously produced.
Description
The invention belongs to building trade and be used to improve the admixture of concrete flowability, more particularly, the present invention is to be the efficient cement water reducing agent that raw material makes with a kind of hydrocarbon fraction oil.
As everyone knows, the mixing material that concrete is made up of cement, sand, stone and water, the way that adopts raising water cement ratio (water and cement weight ratio) promptly to increase the water yield can increase concrete degree of mobilization, improve pumping, but hypervolia, can bring many adverse influences, as prolong cement setting time, reduce concrete final strength, therefore people's research adds a kind of high efficiency water reducing agent in coagulation, can improve concrete degree of mobilization and pumping significantly under the situation that does not increase water consumption; Reduce by 10～20% water consumption, concrete strength is increased substantially.
1938, USP2,141,569 disclose a kind of naphthalene sulphonate formaldehyde thing that contracts, it is still present countries in the world building trades and uses one of maximum high efficiency water reducing agent, compares with ordinary water-reducing agent, also can not delay concrete time of coagulation during the high volume of this water reducer, and early anti pressured intension can improve 100%, and later stage ultimate compression strength can improve 20～50%.In recent years, for the bigger problem of loss of slump that solves high efficiency water reducing agent, succeeded in developing the sulfonate and formaldehyde condenses (USP4457874), poly styrene sulfonate (American Cement Institute, Special Publication 119-8), polyacrylate (DE 3305098A1) of phenol again and with the sulfonate of xylogen, naphthalene, phenol, aniline, naphthylamines, trimeric cyanamide, propylene monomer or the multipolymer of carboxylate salt combination of monomers (spy opens clear 64-113419).The common issue with of above-mentioned high efficiency water reducing agent is that cost of material is expensive, and it is in short supply to originate, and the technology more complicated, so product price is higher, has limited the development of high efficiency water reducing agent.
To propose with coal tar fraction such as naphthalene, naphthalene Residual oil, washing oil, carbolineum etc. be the high efficiency water reducing agent of feedstock production in patent application such as CN1038266A in addition.This class water reducer exists insufficient raw material or the more expensive problem of price equally.
The objective of the invention is that a kind of raw material is easy to get, the simple efficient cement water reducing agent of preparation technology, and can obtain qualified solar oil product simultaneously.
The objective of the invention is to realize by following proposal: with the high petroleum hydrocarbon distillate of aromaticity content is raw material, directly use concentrated acid sulfonation, acid sludge makes required water reducer through hydrolysis, formaldehyde condensation, and the oil product of telling promptly obtains qualified solar oil product through neutralization, distillation.
It is the BTX aromatics sulfonate and formaldehyde condenses type high efficiency water reducing agent that raw material makes that characteristics of the present invention are to adopt 165～365 ℃ of distillates that contain double ring arene＞30%, three ring above aromatic hydrocarbons＜5% and total aromatic hydrocarbons＞50%, and its preparation process is as follows:
1. stock oil is heated to the vitriol oil of dropping 98% after 120～150 ℃, is warming up to 160～80 ℃ then, reacts 1～2 hour, and the vitriolic add-on is 0.6～1.2 times of raw material;
2. after (1) step, reaction product was cooled to 40～80 ℃, be separated into oil product and acid sludge;
3. in isolated acid sludge of (2) step, add entry, little right in 90～110 ℃ of following hydrolysis 0.2～0.5, after hydrolysis finishes, use the formaldehyde solution condensation down in 90～110 ℃, treat the material thickness but still stop condensation can flowing the time, water and acid sludge weight ratio are 0.4～0.8: 1, and formaldehyde and acid sludge weight ratio are 0.2～0.8: 1;
4. add alkali lye in (3) step condensation product, being neutralized to pH under 60～90 ℃ is 8～9, is drying to obtain required water reducer product then;
5. promptly obtain the solar oil of requirement up to specification through alkali lye neutralization, distillation by isolated oil product of (2) step.
Described raw material is 165～365 ℃ the distillate that the Deep Catalytic Cracking process of USP 4980053 propositions obtains, and makes its aromaticity content percentage ratio meter by weight.Total aromaticity content is greater than 50%, and double ring arene is lower than 5% greater than the above aromatic hydrocarbons of 30%, three rings.
Described formaldehyde is that concentration is 37% formaldehyde solution, is the commercially available prod.
In described and the alkali lye used of the condensation product NaOH that is or Ca (OH)
2Alkali lye, when using 30%NaOH alkali lye, its weight ratio is acid sludge: NaOH=1: 1.0～1.8, when using 30%Ca (OH)
2During alkali lye, its weight ratio is acid sludge: Ca (OH)
2=1: 2.0～2.2.
Isolated oil product behind described raw material and the vitriol oil direct reaction behind the remaining acid sludge of natural subsidence separation in 11～24 hours, is neutralized to pH=6～7 with NaOH alkali lye, can obtain qualified solar oil product through atmospheric vacuum distillation method again.
Major advantage of the present invention:
Prior art is to be main raw material with NAPTHALENE FLAKES. (INDUSTRIAL GRADE, alkylnaphthalene, anthracene etc., they all are the dry distillation of coal product or the Organic Chemicals of coking industry, it originates not enough, price is more expensive, the raw material that the present invention uses is the intermediates of the cat-cracker of petroleum refining industry, and cat-cracker is a kind of production equipment of continuous large-scale, can provide a large amount of raw materials for producing high efficiency water reducing agent; The light oil distillate aromaticity content height that obtains by cat-cracker in addition, dark and the destabilization of color, must could obtain qualified diesel product through refining, and common acid-alkali refining is difficult to reduce the aromaticity content of oil product, also produce the acid sludge contaminate environment, but the hydrocarbon ils cut that these aromaticity contents are high then is the desirable feedstock of producing high efficiency water reducing agent, and the present invention can also produce qualified solar oil simultaneously under the situation that reduces pollution; The present invention can be with the catalytic pyrolysis light oil that contains 10～50% stable hydrocarbon without aromatics separation in advance, directly be processed into water reducer, whole technology is fairly simple, raw material cheaply is easy to get in addition, therefore production cost of the present invention is very low, has so just reduced widely to add the cost that the agent concrete particularly adds big pump concrete of dosage and strong concrete; Water reducer salient features of the present invention is better than the water reducer that carbolineum is feedstock production, and when the water reducer amount of water was 1.0%, water-reducing rate can reach 16%.
Advance to describe characteristics of the present invention with example below.
Example 1
In the 2000ml four-hole bottle of agitator, prolong, thermometer and dropping funnel is housed, after 165～261 ℃ of gold-platings of adding catalytic pyrolysis divide oily A (containing stable hydrocarbon 12.1%, mononuclear aromatics 52.5%, double ring arene 35.5%, polycyclic aromatic hydrocarbons 0.1%) 500g to be heated to 140 ℃, add the 500g98% vitriol oil in the dropping mode, under 160 ℃ of temperature, carry out sulfonation reaction.Reduce to room temperature behind the 2h and tell upper strata oily matter 110g, add in the acid sludge behind the 400ml water, add 37% formalin 400ml then,, treat the material thickness but can flow the time 95 ℃ of following condensations at 100 ℃ of following hydrolysis 0.5h.Be cooled to 80 ℃, add 30% sodium hydroxide lye, adjust condenses pH=9, promptly get the 905g powdery product after the spraying drying.After the oily matter of telling after the sulfonation left standstill 12 hours, the micro-acid sludge natural subsidence in the oil product, the oil product after the sedimentation is put into the single port bottle, is neutralized to pH=6 with 30%NaOH, underpressure distillation then, the cut of collecting＜350 ℃ promptly obtains qualified solar oil 98g.
Example 2
Get catalytic pyrolysis distillate A500g and 98% vitriol oil 500g, add 30% calcium hydroxide alkali lye after pressing embodiment 1 sulfonation, hydrolysis, condensation, adjust the pH=9 of condenses, add 200ml water dilution after-filtration, obtain the 522g powder-product after the filtrate spraying drying, obtain 470g calcium sulfate after the filter residue oven dry.The oily matter of telling after the sulfonation obtains solar oil 96g by method neutralization, the distillation of example 1.
Example 3
Get 221～304 ℃ of distillate B of catalytic pyrolysis and (contain stable hydrocarbon 16.1%, mononuclear aromatics 21.2%, double ring arene 62.4%, polycyclic aromatic hydrocarbons 1.1%) 500g, be heated to the 150 back Dropwise 5 00g98% vitriol oils, under 165 ℃, carry out sulfonation reaction, tell upper strata oily matter 102g behind the 1h, in acid sludge, add 400ml water, at 110 ℃ of following hydrolysis 0.5h, add 37% formalin 200ml then, 100 ℃ of following condensations, treat the material thickness but still can flow cooling to 80 ℃, add 30% sodium hydroxide solution, adjust condenses pH=9, spraying drying promptly obtains 905 gram powdery products then.Oily matter after the sulfonation obtains solar oil 92g by method neutralization, the distillation of example 1.
The salient features of 221～304 ℃ of distillate B sulfonation front and back sees Table 1, as shown in Table 1, and the solar oil requirement up to specification that the oily matter after the sulfonation obtains through neutralization, distillation.
Example 4
Get 199～334 ℃ of distillate C of catalytic pyrolysis (containing stable hydrocarbon 44.7%, mononuclear aromatics 23.8%, double ring arene 30.2 %, polycyclic aromatic hydrocarbons 1.3%) 300g, Dropwise 5 00g98% sulfuric acid after being heated to 160 ℃, under 160 ℃, carry out sulfonation reaction, tell upper strata oily matter 163g behind the 1h, in acid sludge, add 400ml water, in 120 ℃ of hydrolysis 0.5h, 37% the formaldehyde solution that adds 450ml then, 110 ℃ of following condensations, the method by example 1 adds alkali lye then, spraying drying promptly obtains the 469g powdery product.The oily matter of telling after the sulfonation obtains solar oil 328g by the neutralization of example 1 method, distillation.
Example 5
Get 199～344 ℃ of distillate D of catalytic pyrolysis (containing stable hydrocarbon 19.4%, mononuclear aromatics 31.3%, double ring arene 47.5%, polycyclic aromatic hydrocarbons 1.8%) 500g, Dropwise 5 00g98% sulfuric acid carries out sulfonation reaction after being heated to 140 ℃, tell upper strata oily matter 144g behind the 1h, in acid sludge, add 400ml water, in 120 ℃ of following hydrolysis 0.5h, 37% the formaldehyde solution that adds 400ml then, 100 ℃ of following condensations, the method by example 1 adds alkali lye then, spraying drying promptly obtains the 908g powdery product.The oily matter of telling after the sulfonation obtains solar oil 130g by the neutralization of example 1 method, distillation.
Example 6
This example is the water reducer that the distillate of employing polycyclic aromatic hydrocarbons＞5% makes.
Get 171～363 ℃ of distillate E of catalytic pyrolysis (containing stable hydrocarbon 23.2%, mononuclear aromatics 29.8%, double ring arene 41.0%, polycyclic aromatic hydrocarbons 5.2%) 500g, drip 98% vitriol oil 500g after being heated to 140 ℃, 160 ℃ of sulfonation reactions, tell upper strata oily matter 92g behind the 2h, press method hydrolysis, condensation, the drying and other steps of example 1 then, obtain the 720g powdery product, the oily matter of telling after the sulfonation obtains solar oil 82g by the neutralization of example 1 method, steaming pomegranate.
Being found out by table 2, is the water reducer that raw material makes with polycyclic aromatic hydrocarbons greater than 5% distillate, substantially flows under the test conditions of low water-cement ratio.
Example 7
This example is a Comparative Examples, is that the water reducer of FDN, AF compares test with water reducer of the present invention and commercially available product grade.
Table 2 is mobile comparative test result of cement paste of measuring by standard GB 8077-87, and it is that water/cement is 0.3 that water cement ratio adopts high efficiency water reducing agent low water-cement ratio commonly used; Table 3 is for containing the concrete comparative test result of water reducer, and every index is measured by standard GB 7034-87.
Find out that by table 2 and table 3 salient features of the BTX aromatics sodium sulfonate formaldehyde condensation products type water reducer that the present invention makes is close with the NAPTHALENE FLAKES. (INDUSTRIAL GRADE water reducer, and is better than the carbolineum water reducer.
Main performance index before and after the table 1. catalytic pyrolysis distillate B sulfonation
| Test event | GB252-81 | After the sulfonation | Before the sulfonation |
| Outward appearance | Transparent | Transparent | Transparent |
| Aromaticity content, % | - | 28.7 | 83.8 |
| Condensation point, ℃ | ＜-10 | -13 | -19 |
| Cetane value | ＞40 | 45 | 18 |
| 10% steams the excess carbon residue | ＜0.3 | 0.18 | |
| Sulphur content, % | ＜0.2 | 0.10 | 0.36 |
| Copper corrosion, 50 ℃/3h | Qualified | Qualified | Qualified |
| Acidity, mgKOH/100ml | ＜10 | 1.3 | 3.2 |
| Existent gum, mg/100ml | ＜70 | ＜2 | 168 |
| Close flash point, ℃ | ＞60 | 78 | 95 |
| Bromine number, gBr/100ml | - | 13 | 9.3 |
| Basic nitrogen ppm | - | 24 | 342 |
The cement million slurry flow test results' of table 2 high efficiency water reducing agent comparison
| Product | Raw material | Addition (g) | Clean slurry degree of mobilization (mm) | Clean slurry flow velocity (mm/s) |
| Example 1 | Catalytic pyrolysis distillate A | 1.0 | 230 | 33 |
| Example 2 | Catalytic pyrolysis distillate A | 1.0 | 220 | 20 |
| Example 3 | Catalytic pyrolysis distillate B | 1.0 | 240 | 40 |
| Example 4 | The catalytic pyrolysis gold-plating divides oily C | 1.0 | 220 | 32 |
| Example 6 | Catalytic pyrolysis distillate D | 1.0 | 230 | 30 |
| Example 7 | Catalytic pyrolysis distillate E | 1.0 | Do not flow | - |
| FDN | NAPTHALENE FLAKES. (INDUSTRIAL GRADE | 0.7 | 221 | 33 |
| AF | Carbolineum | 1.0 | 207 | 20 |
*Clean slurry flow velocity (mm/s)=cement paste trickling section diameter reaches the mean flow rate of 200mm
The comparison of table 3 high efficiency water reducing agent quality index
| Performance index | The high efficiency water reducing agent national standard | Commercially available high efficiency water reducing agent | High efficiency water reducing agent of the present invention | ||||
| Product grade | Acceptable end product | Salable product | FDN | AF | Example 1 product | Example 3 products | |
| Sodium sulphate content % | - | - | 13.0 | 34.8 | 31.3 | 39.6 | |
| Add dosage, % | - | - | 0.7 | 1.0 | 1.0 | 1.0 | |
| Only add dosage ***，％ | - | - | 0.61 | 0.65 | 0.69 | 0.60 | |
| Slump *，％ | 6.0±1 | 6.0±1 | 5.0/5.0 | 6.0/6.0 | 6.0/6.0 | 6.0/5.0 | |
| Water-reducing rate, % | ＞12 | ＞10 | 14 | 10 | 17 | 18 | |
| The bleeding rate ratio, the % air content, the % presetting period is poor, and min doubts time difference, min eventually | ＜100 | ＜100 | 71 | - | 60 | 60 | |
| ＜3.0 | ＜4.0 | - | 1.78 | 1.03 | 1.30 | ||
| -60～+90 | -60～+120 | -8 | - | -31 | -18 | ||
| -60～+90 | -60～+120 | -6 | - | -26 | -13 | ||
| Ultimate compression strength | 1D 3D 7D 28D | ＞140 | ＞130 | 162 | 149 | 157 | 188 |
| ＞130 | ＞125 | 153 | 157 | 162 | 164 | ||
| ＞125 | ＞120 | 133 | 128 | 136 | 124 | ||
| ＞120 | ＞115 | 128 | 113 | 121 | 115 | ||
*Oblique line is blank concrete slump down;
*Cement: 525 reference cements;
* *Deduction adds dosage behind the sodium sulfate.
Claims (4)
1. efficient cement water reducing agent, it is characterized in that with contain double ring arene greater than the above aromatic hydrocarbons of 30%, three rings be lower than 5% and total aromaticity content be the BTX aromatics sulfonate and formaldehyde condenses type cement water reducing agent that raw material makes greater than 50% 165～365 ℃ distillate, its preparation process:
(1) add 98% vitriol oil after raw material is heated to 120～150 ℃, be warming up to 160～180 ℃ then, reacted 1～2 hour, the vitriolic add-on is 0.6～1.2 times of raw material,
(2) be separated into oil product and acid sludge after the reaction product of (1) is cooled to 40～80 ℃, the oil product of telling obtains qualified solar oil by neutralization, distillation,
(3) in isolated acid sludge of (2) step, add entry, 90～110 ℃ of following hydrolysis 0.2～0.5 hour, hydrolysis finishes the back and uses the formaldehyde solution condensation down in 90～110 ℃, treat the material thickness but still stop condensation can flowing the time, water and acid sludge weight ratio are 0.4～0.8: 1, formaldehyde and acid sludge weight ratio are 0.2～0.8: 1
(4) add alkali lye in (3) step condensation product, being neutralized to pH under 60～90 ℃ is 8～9, and drying can obtain required product then.
2. according to the described water reducer of claim 1, the alkali lye of using with condensation product in it is characterized in that is NaOH or Ca (OH)
2The aqueous solution.
3. according to claim 1 or 2 described water reducers, the alkali lye amount of using with condensation product in it is characterized in that is acid sludge: NaOH=1: 1.0～1.8 (weights).
4. according to claim 1 or 2 described water reducers, the alkali lye amount with condensation product during it will be levied and be is acid sludge: Ca (OH)
2=1: 2.0～2.2 (weights).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96106515A CN1062534C (en) | 1996-06-14 | 1996-06-14 | Efficient concrete water-reducing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96106515A CN1062534C (en) | 1996-06-14 | 1996-06-14 | Efficient concrete water-reducing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1168360A CN1168360A (en) | 1997-12-24 |
| CN1062534C true CN1062534C (en) | 2001-02-28 |
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ID=5119229
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96106515A Expired - Fee Related CN1062534C (en) | 1996-06-14 | 1996-06-14 | Efficient concrete water-reducing agent |
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| Country | Link |
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| CN (1) | CN1062534C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1084309C (en) * | 1998-05-28 | 2002-05-08 | 中国石化安庆石油化工总厂 | Preparation method of petroleum series high-effeciency concrete water reducer |
| CN1083808C (en) * | 1999-09-14 | 2002-05-01 | 中国科学院广州化学研究所 | Process for preparing water reducer of cement |
| CN101824128B (en) * | 2010-04-16 | 2011-11-23 | 南京瑞迪高新技术公司 | Beta-naphthol produced waste liquid modified amido sulfoacid series high-efficiency water reducer and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1038266A (en) * | 1988-06-09 | 1989-12-27 | 河北省水利厅工程局外加剂厂 | Concrete high efficiency water reducing agent and concrete retarding type high efficiency water reducing agent |
| US4980053A (en) * | 1987-08-08 | 1990-12-25 | Research Institute Of Petroleum Processing, Sinopec | Production of gaseous olefins by catalytic conversion of hydrocarbons |
-
1996
- 1996-06-14 CN CN96106515A patent/CN1062534C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4980053A (en) * | 1987-08-08 | 1990-12-25 | Research Institute Of Petroleum Processing, Sinopec | Production of gaseous olefins by catalytic conversion of hydrocarbons |
| CN1038266A (en) * | 1988-06-09 | 1989-12-27 | 河北省水利厅工程局外加剂厂 | Concrete high efficiency water reducing agent and concrete retarding type high efficiency water reducing agent |
Non-Patent Citations (1)
| Title |
|---|
| 混凝土外加剂概论 1985.1.1 清华大学出版社 * |
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| CN1168360A (en) | 1997-12-24 |
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