CN1067259A - Tar oil type high-concentration water-coal slurry additive and production technique - Google Patents
Tar oil type high-concentration water-coal slurry additive and production technique Download PDFInfo
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- CN1067259A CN1067259A CN 91103371 CN91103371A CN1067259A CN 1067259 A CN1067259 A CN 1067259A CN 91103371 CN91103371 CN 91103371 CN 91103371 A CN91103371 A CN 91103371A CN 1067259 A CN1067259 A CN 1067259A
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Abstract
The invention relates to the production technique of tar oil type high-concentration water-coal slurry additive.The general formula of its additive is as follows:
T in the formula, M, n demarcate in specification sheets.
Additive with the present invention produces can prepare and contain 30% water, and 70% coal dust a kind of flowed, cleaning, clean liquid fuel---coal water slurry.This viscosity of coal-water slurry can be controlled in below the 1500mPaS, and the volume of additive is 0.3～1.0%.
Description
The invention belongs to a kind of tar oil type high-concentration water-coal slurry additive and the production technique that are starting raw material with 200～360 ℃ of fractions of tar.Can produce with the additive of this explained hereafter and to contain 30% water, the high-concentration coal-water slurry of 70% coal.
In the preparation of high-concentration coal-water slurry, additive has very crucial effect.This technology is the gordian technique of producing additive.
For many years, the production of slurries additive agent has many precedents.As, Chinese patent No85109233 has introduced a kind of special oxyalkylated amino-polyether additive and preparation technology thereof of containing.US Patent No 4415338 is introduced bitter edible plant sulfonic acid and formaldehyde polycondensate as slurries additive agent.Japanese Patent No58042694 has introduced a kind of rudimentary ammonium salt of alkane methyl hydrochlorate formula of vinylbenzene cis-butenedioic anhydride multipolymer.US Patent No 4457762 has been introduced aryl acid and formaldehyde condensation products.Europe patent No109740 has introduced the olefin oxide multipolymer.Japanese Patent No58111893 has introduced alkyl alcohol and ethylene oxide copolymer.Once used bitter edible plant sulfonic acid polycondensate and sulfonation humic acid during China " six or five " as slurries additive agent.The additive and the preparation technology thereof that more than exemplify are each has something to recommend him.
Coal water slurry is a kind of novel clean liquid fuel, can replaces oil fuel directly to burn.Look forward to its development prospect, must seek a kind of new additive agent that meets China's actual conditions.
The present invention compares with more above-mentioned additives, and its principal character is with 200～230 ℃, 300～360 ℃ fractions of tar, respectively with being starting raw material.The raw material sources of Additive Production have been widened.And, this raw material sources are extensive, inexpensive, the additive tool volume that makes is few, and good dispersiveness is arranged, the pulping rear stability is good, so can reduce the advantages such as consumption of stablizer in the coal water slurry.
In the present invention, so, produce the required additive of coal water slurry that satisfies different coals, different gradation because the complicacy of starting raw material component is particularly suitable for the method with the adjustment feed ratio.Simultaneously, just use cost, reach that volume is few, the purpose of best results for what reduce additive.Tar oil type additive with the present invention produces can use separately, also can be composite with coal dust, and also can be composite with bitter edible plant sulfonic formaldehyde condensation compound, alkyl phenol sulfonic yuban and other suitable anion surfactant.
The slurries additive agent that the present invention relates to is characterized in that the finished product should contain following general structure (I):
In the formula: T represents the fraction obtained from tar, its average molecular weight is 80～100.
M: can be K
+, Na
+, NH
+ 4, Ca
++, Mg
++
N: the expression polymerization degree, round numbers 1～20.
In logical formula I, all contain a sulfo group on each T group, and be irregular alignment on molecular chain.Sulphonating agent can be used oleum, the vitriol oil, sodium pyrosulfate and sulphite.
Technology characteristics of the present invention is: starting raw material through purification, sulfonation, absorption, polycondensation, neutralization, concentrate and drying is made pulverous additive.Also can directly use without concentrating with the exsiccant liquid polymers.
The feature of its purification is, so tar cuts all must be rejected the fraction below 200 ℃.
The feature of its sulfonation reaction is that the mol ratio of starting raw material and sulphonating agent is 1: 1.0-2.0, preferably 1: 1.3-1.7.Sulfonation temperature is at 100-170 ℃.The waste gas that sulfonation reaction produces must be handled, and its treatment process is directly to burn or solution absorption.
The feature of its polycondensation is that the ratio of starting raw material and formaldehyde is 1: 0.5-1.0, preferably 1: 0.8-0.9.Condensation temperature is controlled at 80-110 ℃.
Neutralization reaction available hydrogen potassium oxide, salt of wormwood, sodium hydroxide, yellow soda ash, calcium hydroxide or ammoniacal liquor.PH is controlled at 7-12, preferably 7-9.
It should be noted that the off gas treatment of sulfonation reaction especially.Treatment process available hydrogen sodium hydroxide solution, aqua calcis or ammoniacal liquor absorb, and also can directly burn.
As can adopt the absorption that circulates of absorption tower, washing tower or jet-pump with absorption process.
The tar oil type slurries additive agent that makes with this production technique can be made solid shape carbon content and easily flow the coal water slurry of cleaning at 64-75%.This coal water slurry is at 100S
-1Under the shearing rate, viscosity controller preferably is controlled at below the 800mPaS below 1500mPaS.The volume of additive is 0.3～1.0%.Compare with other additive, its good dispersity, good to the grating requirement tolerance of coal dust, product is nontoxic.
Embodiment one
The there-necked flask that electronic stirring, condenser, air-washer and thermometer are housed is put on heating unit.Taking by weighing the washing oil (230～300 ℃ of fractions of tar) that 1.5 moles industry purified drops in the there-necked flask.Add 2.25 mol sulfuric acid, reaction 5～6 hours down at 150 ℃.After sulfonation finishes, cooling.Under 80 ℃ of conditions, add 1.5 moles formaldehyde, and 100 ℃ of insulations three hours.Polycondensation finishes, and is neutralized to PH8.0 with sodium hydroxide, puts into oven for drying, and dry back is taken out and taken advantage of hot grinding powder.Get sample 1
#
With sample 1
#Do pulp-making test, must descend column data:
| Coal | Volume (%) | Dry coal content (%) | Viscosity (100S －1） mPaS |
| The village, Yongding, Shanxi floatation clean coal | 0.5 | 65.8 | 1126.8 |
| Hunan grace mouth clean fine coal | 0.5 | 65.5 | 997.8 |
| The Huainan is washed and is stained with coal | 0.4 | 67.5 | 1167.5 |
| Fushun tiger platform selects cleaned coal | 0.3 | 66.6 | 1089 |
| Smalls is washed in the west, Fushun in the open | 0.3 | 64 | 584.9 |
| Zaozhuang Aug. 1st floatation clean coal | 0.3 | 65.5 | 631.4 |
Embodiment two
Utilize embodiment one, the sample of acquisition is got corrective and adding is levigate, and fineness is at the coal dust below-200.Corrective and coal dust ratio be oven dry jointly in 1: 3, porphyrize, sample 2
#Through the sample of handling like this, rate of dispersion is better than sample 1
#Under equal conditions, the pulping speed trial is done in the laboratory.The result is as follows:
| Sample | Coal | Volume (%) | Concentration (%) | Viscosity (100S －1） mPaS | Achievement time S |
| 1 | Zaozhuang Aug. 1st | 0.3 | 66.5 | 1106 | 185 |
| 2 | Floatation clean coal | 1.0 | 66.4 | 1046 | 148 |
Embodiment three
With 1 of embodiment one
#Sample 100 grams, sodium salt 10 grams that add naphthalene sulfonic acidformaldehyde condensation product are re-dubbed 3
#Sample carries out pulp-making test, and the result is as follows:
| Coal | Volume (%) | Concentration (%) | Viscosity (100S －1） mPaS |
| The Aug. 1st floatation clean coal | 0.3 | 65.5 | 593 |
Claims (6)
1, a kind of tar oil type high-concentration water-coal slurry additive and production technique, it is characterized in that with 200～230 ℃ in tar, 230～300 ℃, 300～360 ℃ fraction starting raw materials, through purification, sulfonation, waste gas absorption, polycondensation, neutralization, concentrate and dry and make the tar oil type slurries additive agent, its general structure (I) is:
In the formula: T represents the fraction of getting in the tar, and average molecular weight is 80～200,
M: can be K
+, Na
+, NH4
+, Ca
++, Mg
++,
N: the expression polymerization degree, round numbers 1～20,
Each T group all contains sulfo group in general formula (I), and is irregular alignment, and sulphonating agent can be used oleum, the vitriol oil, sodium pyrosulfate and sulphite.
2,, it is characterized in that purifying used tar cuts and must remove fraction below 200 ℃ according to said tar oil type high-concentration water-coal slurry additive of claim 1 and production technique.
3, according to said tar oil type high-concentration water-coal slurry additive of claim 1 and production technique, the mol ratio that it is characterized in that sulfonation reaction starting raw material and sulphonating agent is 1: 1.0～2.0, best 1: 1.3～1.7, its sulfonation temperature is at 100～170 ℃, the waste gas that sulfonation produces must be handled, and treatment process is with burning method and solution absorption method;
4, according to said tar oil type high-concentration water-coal slurry additive of claim 1 and production technique, the feed ratio that it is characterized in that polycondensation starting raw material and formaldehyde is 1: 0.5～1.0, and best proportioning is 1: 0.8～0.9, and condensation temperature is at 80～110 ℃.
5, according to said tar oil type high-concentration water-coal slurry additive of claim 1 and production technique, it is characterized in that neutralization reaction control pH value 7～12, the best is 7～9.
6, it is characterized in that according to said tar oil type high-concentration water-coal slurry additive of claim 1 and production technique this additive can use separately, also can be composite with other anion surfactant and coal dust, improve performance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91103371 CN1030576C (en) | 1991-05-28 | 1991-05-28 | Tar oil type high-concentration water-coal slurry additive and its process for production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91103371 CN1030576C (en) | 1991-05-28 | 1991-05-28 | Tar oil type high-concentration water-coal slurry additive and its process for production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1067259A true CN1067259A (en) | 1992-12-23 |
| CN1030576C CN1030576C (en) | 1995-12-27 |
Family
ID=4906065
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91103371 Expired - Fee Related CN1030576C (en) | 1991-05-28 | 1991-05-28 | Tar oil type high-concentration water-coal slurry additive and its process for production |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1030576C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101451082B (en) * | 2008-12-30 | 2012-02-29 | 中国科学院工程热物理研究所 | Method for preparing bituminous coal slurry |
| CN101735870B (en) * | 2009-12-16 | 2013-06-19 | 北京海淀华煤水煤浆技术开发中心 | Coal water slurry additive and preparation method and application thereof |
| CN105062652A (en) * | 2015-08-21 | 2015-11-18 | 太原理工大学 | Method for preparing surfactant for water-coal slurry from waste lubricating oil |
| CN105647604A (en) * | 2016-01-23 | 2016-06-08 | 李俏 | Modified wash oil coal water slurry additive and preparing method thereof |
| CN105695001A (en) * | 2016-02-17 | 2016-06-22 | 兖矿水煤浆气化及煤化工国家工程研究中心有限公司 | Tar-type coal water slurry additive prepared from composite raw materials and production technology of tar-type coal water slurry additive |
| CN110804141A (en) * | 2019-11-19 | 2020-02-18 | 安徽鑫固环保股份有限公司 | Method for synthesizing coal water slurry dispersant by using coking wash oil |
| CN111690447A (en) * | 2020-05-11 | 2020-09-22 | 万华化学（宁波）有限公司 | Coal water slurry additive and preparation method and application thereof |
| CN115181595A (en) * | 2022-07-14 | 2022-10-14 | 中国科学院宁波材料技术与工程研究所 | Phenolic oil modified coal water slurry dispersant, and preparation method and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103965981B (en) | 2013-01-31 | 2016-05-25 | 通用电气公司 | The apparatus and method of preparation water-coal-slurry |
-
1991
- 1991-05-28 CN CN 91103371 patent/CN1030576C/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101451082B (en) * | 2008-12-30 | 2012-02-29 | 中国科学院工程热物理研究所 | Method for preparing bituminous coal slurry |
| CN101735870B (en) * | 2009-12-16 | 2013-06-19 | 北京海淀华煤水煤浆技术开发中心 | Coal water slurry additive and preparation method and application thereof |
| CN105062652B (en) * | 2015-08-21 | 2017-09-05 | 太原理工大学 | A kind of method of water-coal-slurry surfactant is produced from waste lubricating oil |
| CN105062652A (en) * | 2015-08-21 | 2015-11-18 | 太原理工大学 | Method for preparing surfactant for water-coal slurry from waste lubricating oil |
| CN107267238A (en) * | 2016-01-23 | 2017-10-20 | 李俏 | A kind of preparation method of modified washing oil slurries additive agent |
| CN105647604A (en) * | 2016-01-23 | 2016-06-08 | 李俏 | Modified wash oil coal water slurry additive and preparing method thereof |
| CN107488473A (en) * | 2016-01-23 | 2017-12-19 | 李俏 | A kind of preparation method of modified washing oil slurries additive agent |
| CN107653013A (en) * | 2016-01-23 | 2018-02-02 | 李俏 | A kind of preparation method of modified washing oil slurries additive agent |
| CN107267238B (en) * | 2016-01-23 | 2019-10-01 | 南理工泰兴智能制造研究院有限公司 | A kind of preparation method of modified washing oil slurries additive agent |
| CN107653013B (en) * | 2016-01-23 | 2019-10-18 | 司传煜 | A kind of preparation method of modified washing oil slurries additive agent |
| CN105695001A (en) * | 2016-02-17 | 2016-06-22 | 兖矿水煤浆气化及煤化工国家工程研究中心有限公司 | Tar-type coal water slurry additive prepared from composite raw materials and production technology of tar-type coal water slurry additive |
| CN110804141A (en) * | 2019-11-19 | 2020-02-18 | 安徽鑫固环保股份有限公司 | Method for synthesizing coal water slurry dispersant by using coking wash oil |
| CN111690447A (en) * | 2020-05-11 | 2020-09-22 | 万华化学（宁波）有限公司 | Coal water slurry additive and preparation method and application thereof |
| CN115181595A (en) * | 2022-07-14 | 2022-10-14 | 中国科学院宁波材料技术与工程研究所 | Phenolic oil modified coal water slurry dispersant, and preparation method and application thereof |
| CN115181595B (en) * | 2022-07-14 | 2023-10-20 | 中国科学院宁波材料技术与工程研究所 | Phenol oil modified coal water slurry dispersing agent and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1030576C (en) | 1995-12-27 |
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