CN101029259A - Desulfurized hydrated coking slurry formula and its production - Google Patents
Desulfurized hydrated coking slurry formula and its production Download PDFInfo
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- CN101029259A CN101029259A CNA2006100351431A CN200610035143A CN101029259A CN 101029259 A CN101029259 A CN 101029259A CN A2006100351431 A CNA2006100351431 A CN A2006100351431A CN 200610035143 A CN200610035143 A CN 200610035143A CN 101029259 A CN101029259 A CN 101029259A
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- water
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
- C10L1/326—Coal-water suspensions
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
A desulfurized hydrous coke slurry composition consists of petrol coke 55-75wt%, water 24-44wt% and additive 0.1-2wt%. The additive contains dispersant with hydrous coke slurry viscosity decreasing, stabilizer for preventing hydrous coke slurry from producing hard deposits and desulfurizer with sulfur dioxide discharge decreaing. It has better fluidity and stability and less sulfur dioxide.
Description
Technical field
The present invention relates to a kind of burnt slurry of water and preparation technology thereof who is used for firing system, more particularly, the present invention relates to reduce desulfurized hydrated coking slurry and the preparation technology thereof that sulfurous gas takes off discharging after a kind of burning.
Background technology
The burnt slurry of water is that the byproduct refinery coke with petroleum refining is a raw material, adds the liquid fuel that entry and additive become through specific prepared.It can be used as with fuel oil and/or combustion gas is the alternative fuel of the thermal hardware of fuel, in general, and the alternative 1 ton of crude oil of per 1.18 tons of refinery cokes, thereby apply the burnt slurry of water and can save the petroleum resources of shortage, realize the reasonable resources utilization.Type approval test proves, the expense that oil-firing boiler is produced steam is 152.75 yuan of/ton steam (crude oil price is by 2350 yuan/ton), and the expense that changes the burnt slurry production of burning petroleum steam is that (the refinery coke price is by 810 yuan/ton for 96.52 yuan of/ton steam, other adds slurrying and other expenses), the burnt slurry of combustion water reduces expenses 36.81% than fuel oil.Flue dust and all not high (SO of sulfurous gas in the stack gas emissions of the burnt slurry burning of water back
2Content is 201.7mg/m
3Mark, smoke content is 43.0mg/m
3Mark), economic benefit and obvious social benefit.
The refinery coke component is a hydrocarbon polymer, and from structure with can be divided into needle coke, sponge coke, shot coke and coke breeze in appearance, it is under the seasoning state, moisture content accounts for 3%, and ash content is about 1.12%, the about 30.35MJ/kg of thermal value, volatile matter is about 11.03%, and Hardgrove grindability index (HGI) is 80.The burnt slurry of water makes by refinery coke is mixed and add suitable additive with water.
Chinese patent application CN200410014722.9 discloses the burnt slurry of a kind of composite nano inoganic coal water slurry/water stablizer, this stablizer is mixed by fibrous inorganic nano-particle and spherical inorganic nano-particle, particle diameter is the 10-100 nanometer, the length-to-diameter ratio of fibrous inorganic nano-particle is 50-200, and the mass percent of fibrous inorganic nano-particle and spherical inorganic nano-particle is 10: 90-90: 10.The burnt slurry of this water stablizer utilizes the surface property of nanoparticle uniqueness, will be spherical and the fibrous nano particle carry out compositely, the multiple stabilizing effect of collaborative performance shows to show and improves the stability that water coal/Jiao starches.
Chinese patent CN99107794.6 discloses a kind of refinery coke water slurry body composition with the grizzle modification, and this slurry composition comprises: (1) petroleum coke powder; (2) rudimentary coal dust, its median size 36-45 μ m, its consumption is the 10-100% of petroleum coke powder weight; (4) water, its consumption are the 40-60% that petroleum coke powder adds rudimentary coal dust gross weight; (4) additive, this additive is the tensio-active agent that is selected from anionic, comprising: Sulfonates, be selected from Sodium dodecylbenzene sulfonate or sodium polystyrene sulfonate, perhaps phosphoric acid ester is selected from phosphoric acid C12-18 alkyl monoester or phosphoric acid C12-18 alkyl diester; Perhaps select the tensio-active agent of non-ionic type for use, as oxyethane and epoxy propane copolymer; The mixture of perhaps selecting for use two or three in the above-mentioned various additive to form, the consumption of additive are every kilogram of solids butt 2-10 gram.This patent mixed coal powder in petroleum coke powder has improved the performance of refinery coke water pulping, has improved the stability of slurry composition.
Chinese patent CN00113911.8 discloses the gasification slip that a kind of coal, refinery coke, additive and water are formed, its preparation method is coal, refinery coke, water and additive to be added grinding plant simultaneously prepare slip, promptly adopt the wet-milling pulping process one time, the granularity 100% of the used coal of preparation slip is less than 0.9mm, 30～80% less than 0.76mm, the granularity 100% of refinery coke is less than 0.6mm, and 50～90% less than 0.076mm.This preparation method can directly produce coke-water slurry to generate gas on existing coal water slurry preparation facilities, and can be applicable in the unstripped gas preparations such as synthetic ammonia and synthesizing methanol.
Prior art does not so far still provide a kind of burnt slurry of water that has the good stability energy and can reduce sulfur dioxide emissions after burning.
Summary of the invention
The purpose of this invention is to provide a kind of burnt slurry of water that hard-caked sediment does not take place and can reduce the burning back sulfur in smoke of discharging.
Another object of the present invention provides a kind of processing method for preparing the burnt slurry of above-mentioned water.
For realizing above-mentioned goal of the invention, on the one hand, the invention provides a kind of desulfurized hydrated coking paste composition, the burnt paste composition of this water comprises refinery coke, water and additive, in the quality percentage composition, in the burnt paste composition of this water, refinery coke accounts for 55-75%, and water accounts for 24-44%, and additive accounts for 0.1-2%.Additive in the burnt paste composition of water of the present invention further comprises the dispersion agent that reduces the burnt paste composition slurry of water viscosity, the stablizer of the burnt paste composition generation of anti-sealing hard-caked sediment and the sweetening agent that reduces burning back sulfur dioxide emissions.
In the burnt paste composition of above-mentioned water; dispersion agent can be one or more aniorfic surfactant, for example: fatty acid methyl ester (utilizing oily soap stock to produce); sodium alkyl benzene sulfonate; alkyl benzene calcium sulfonate; dioctyl sodium sulfosuccinate; N-acyl group N-methyltaurine sodium; sulfonation Succinic Acid di-isooctyl sodium salt; the JE-2 emulsifying agent; dispersant with high efficiency FN; sodium lauryl sulfate; polyoxyethylene sodium sulfate (AES); polyoxyethylenated alcohol sodium sulfate; polyoxyethylene ether phosphate (aniorfic surfactant); phosphoric acid ester; tricresyl phosphate (2-Ethylhexyl Alcohol) ester etc.Preferably sulfonated humic acid sodium and/or sodium lignosulfonate.Among the present invention, the main effect of dispersion agent is to reduce the burnt slurry of water slurry viscosity, makes it to present the inviscid flow build.
In the burnt paste composition of above-mentioned water, stablizer can be one or more the inorganic electrolyte of positively charged ion salt, for example saltpetre, phosphoric acid salt.Preferred stablizer is ferrous sulfate and/or tripoly phosphate sodium STPP.Among the present invention, the main effect of stablizer is a compression double electric layer, reduces electrostatic repulsion forces, impels the coalescent stable suspersion of refinery coke grain in water, and hard-caked sediment does not take place.
In the burnt paste composition of above-mentioned water, sweetening agent can be Calcium Chloride Powder Anhydrous, also can be other sweetening agent, for example gac, zinc oxide, ferric oxide etc.Preferred sweetening agent is a Calcium Chloride Powder Anhydrous.Among the present invention, it is to reduce the burning back sulfur in smoke of discharging that sweetening agent mainly acts on, and reduces atmospheric pollution.
Further, in the burnt paste composition of water of the present invention, in the quality percentage composition, refinery coke is preferably 60-70%, and water is preferably 29-39%, and additive is preferably 0.2-1%
Further, in the burnt paste composition of water of the present invention, in the quality percentage composition, dispersion agent is preferably 0.05-1.5%, and stablizer is preferably 0.02-1.0%, and sweetening agent is preferably 0.05-0.5%.
Except that refinery coke, water and additive, the burnt paste composition of water of the present invention can further include other component, for example coal dust or other combustiblematerials.Except that dispersion agent, stablizer and sweetening agent, the additive of the burnt slurry of water of the present invention can further include the additive of other type, as ignition dope.
On the other hand, the present invention also provides a kind of processing method for preparing the burnt paste composition of above-mentioned water, and this method comprises:
(1) block refinery coke is carried out mechanical disintegration, obtain petroleum coke powder;
(2) above-mentioned petroleum coke powder is carried out weighing;
(3) petroleum coke powder through weighing adds dispersion agent, sweetening agent and water in proportion, carries out wet ball-milling slurrying, forms the burnt slurry of initial state water;
(4) the burnt slurry of above-mentioned resulting initial state water is filtered, stirs;
(5) the burnt slurry of the initial state water that stirs is carried out homogeneous and adds stablizer stirring.
In the superincumbent processing method, step (1) can be in two steps or multistep carry out.If carry out in two steps, then the first step is block refinery coke to be pulverized be the petroleum coke powder of larger particles, and second step was the petroleum coke powder of larger particles further to be pulverized be more short grained petroleum coke powder.
Compared with prior art, the burnt paste composition of water of the present invention is owing to contain dispersion agent and stablizer, thereby has better flowability and stability; The burnt paste composition of water of the present invention is owing to contain sweetening agent, and can reduce the burning back sulfur in smoke of discharging, and reduction is to atmospheric pollution.In addition, because additive amount is less, and nontoxic, thereby complete compliance with environmental protection requirements.
Below, in conjunction with the accompanying drawings and embodiment, further specify the present invention, but the present invention is not limited to these embodiments, any on essence spirit of the present invention improvement or substitute, still belong to scope required for protection in claims of the present invention.
Description of drawings
Fig. 1 is the process flow diagram of the burnt paste composition of preparation water of the present invention.
Embodiment
Embodiment 1
Press refinery coke: water: the burnt slurry of mass percent preparation water of additive=65.5: 34: 0.44, wherein, the concrete content of each component sees Table 1 in the additive.
Table 1
| Title | Classification | Add-on | |
| Embodiment 1 | Sulfonated humic acid sodium | Dispersion agent | 0.3％ |
| Ferrous sulfate | Stablizer | 0.04％ | |
| Calcium Chloride Powder Anhydrous | Sweetening agent | 0.1％ | |
| Embodiment 2 | Sodium lignosulfonate | Dispersion agent | 0.3％ |
| Tripoly phosphate sodium STPP | Stablizer | 0.2％ | |
| Calcium Chloride Powder Anhydrous | Sweetening agent | 0.1％ | |
| Embodiment 3 | Sulfonated humic acid sodium | Dispersion agent | 0.7％ |
| Ferrous sulfate | Stablizer | 0.1％ | |
| Calcium Chloride Powder Anhydrous | Sweetening agent | 0.3％ | |
| Embodiment 4 | Sodium lignosulfonate | Dispersion agent | 1.0％ |
| Tripoly phosphate sodium STPP | Stablizer | 0.5％ | |
| Calcium Chloride Powder Anhydrous | Sweetening agent | 0.2％ |
The process for preparation of the burnt slurry of above-mentioned water sees also pulping process flow figure shown in Figure 1, and its detailed process is:
(1) block refinery coke is carried out one-time mechanical and be crushed to granularity 8mm;
(2) will be transported to crusher with rotary conveyor through the refinery coke of primary fragmentation and carry out secondary breaking, reach the powdery of granularity 2mm;
(3) refinery coke after the pulverizing is transported to the weighing belt consecutive weighings by rotary conveyor;
(4) adding additive (dispersion agent and sweetening agent) and water in proportion through the petroleum coke powder of weighing sends into ball mill and carries out continuous wet ball-milling slurrying;
(5) petroleum coke powder, water, additive grind in brute force through ball mill and form the burnt slurry of initial state water down;
(6) colour strainer of the burnt slurry of initial state water in being installed in transport pipe filters;
(7) the burnt slurry of the initial state water after the filtration is equipped with the stirred pot stirring of agitator with the spiral pump input;
(8) the burnt slurry of the initial state water that stirs carries out quality test;
(9) the qualified burnt slurry of initial state water stirs with strengthening pump input homogeneous jar and adding additive (stablizer) in proportion.(stirring action not only makes the burnt slurry of water condition even, and in the pumping and whipping process of system, the burnt slurry of water is subjected to motion repeatedly and shears, and has strengthened acting between additive and refinery coke powder surface, has effectively improved slurry rheology.)；
(10) the burnt slurry of the water through being up to the standards is equipped with the conservation tank of agitator with the pump input or daily slurry jar that agitator is equipped with in input enters firing system by pot strainer under whipped state.
Quality index to the burnt slurry of prepared water detects, and each quality index is as follows:
Concentration: 66 ± 1% (in mass);
Viscosity: 300-800mPa.s;
Fineness: granularity is not more than 10% greater than the particle of 74 μ m;
Proportion: 1.12;
Stability: 1 month (hard-caked sediment does not take place).
Embodiment 2
Press refinery coke: water: the burnt slurry of mass percent preparation water of additive=65.4: 34: 0.6, wherein, the concrete content of each component sees Table 1 in the additive therefor, and process for preparation is with embodiment 1.
Embodiment 3
Press refinery coke: water: the burnt slurry of mass percent preparation water of additive=60.9: 38: 1.1, wherein, the concrete content of each component sees Table 1 in the additive therefor, and process for preparation is with embodiment 1.
Embodiment 4
Press refinery coke: water: the burnt slurry of mass percent preparation water of additive=68.3: 30: 1.7, wherein, the concrete content of each component sees Table 1 in the additive therefor, and process for preparation is with embodiment 1.
Claims (10)
1, a kind of desulfurized hydrated coking paste composition, the burnt paste composition of this water comprises refinery coke, water and additive, it is characterized in that, in the quality percentage composition, in the burnt paste composition of described water, described refinery coke accounts for 55-75%, described water accounts for 24-44%, and described additive accounts for 0.1-2%; And described additive further comprises the dispersion agent that reduces the burnt paste composition slurry of described water viscosity, the stablizer that prevents the burnt paste composition generation of described water hard-caked sediment and the sweetening agent that reduces burning back sulfur dioxide emissions.
2, the burnt paste composition of water as claimed in claim 1 is characterized in that described dispersion agent is an aniorfic surfactant.
3, the burnt paste composition of water as claimed in claim 2 is characterized in that described dispersion agent is sulfonated humic acid sodium and/or sodium lignosulfonate.
4, the burnt paste composition of water as claimed in claim 1 is characterized in that described stablizer is the inorganic electrolyte of positively charged ion salt.
5, the burnt paste composition of water as claimed in claim 4 is characterized in that described stablizer is ferrous sulfate and/or tripoly phosphate sodium STPP.
6, the burnt paste composition of water as claimed in claim 1 is characterized in that described sweetening agent is a Calcium Chloride Powder Anhydrous.
7, the burnt paste composition of water as claimed in claim 1 is characterized in that, in the quality percentage composition, in the burnt paste composition of described water, described refinery coke accounts for 60-70%, and described water accounts for 29-39%, and described additive accounts for 0.2-1%.
8, as the burnt paste composition of the described water of one of claim 1-7, it is characterized in that, in the quality percentage composition, in the burnt paste composition of described water, described dispersion agent accounts for 0.05-1.5%, described stabilizer comprises 0.02-1.0%, and described sweetening agent accounts for 0.05-0.5%.
9, a kind of preparation is as the processing method of the burnt paste composition of the described water of one of claim 1-8, and this method comprises:
(1) block refinery coke is carried out mechanical disintegration, obtain petroleum coke powder;
(2) above-mentioned petroleum coke powder is carried out weighing;
(3) petroleum coke powder through weighing adds dispersion agent, sweetening agent and water in proportion, carries out wet ball-milling slurrying, forms the burnt slurry of initial state water;
(4) the burnt slurry of above-mentioned resulting initial state water is filtered, stirs;
(5) the burnt slurry of the initial state water that stirs is carried out homogeneous and adds stablizer stirring.
10, processing method as claimed in claim 9, it is characterized in that, described step (1) is carried out in two steps, wherein, the first step is block refinery coke to be pulverized be the petroleum coke powder of larger particles, and second step was the petroleum coke powder of larger particles further to be pulverized be more short grained petroleum coke powder.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100351431A CN100556996C (en) | 2006-04-24 | 2006-04-24 | Desulfurized hydrated coking slurry formula and preparation technology thereof |
| PCT/CN2007/001318 WO2007124681A1 (en) | 2006-04-24 | 2007-04-23 | Desulfurizing coke-water slurry and process for preparation thereof |
| MYPI20084261A MY157996A (en) | 2006-04-24 | 2008-10-24 | Desulfurizing coke-water salurry and process for preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100351431A CN100556996C (en) | 2006-04-24 | 2006-04-24 | Desulfurized hydrated coking slurry formula and preparation technology thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101029259A true CN101029259A (en) | 2007-09-05 |
| CN100556996C CN100556996C (en) | 2009-11-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100351431A Active CN100556996C (en) | 2006-04-24 | 2006-04-24 | Desulfurized hydrated coking slurry formula and preparation technology thereof |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN100556996C (en) |
| MY (1) | MY157996A (en) |
| WO (1) | WO2007124681A1 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101225335B (en) * | 2008-01-27 | 2011-06-22 | 中国石油化工集团公司 | Preparation method of water coke slurry for gasification |
| CN102268306A (en) * | 2010-06-02 | 2011-12-07 | 深圳市赛尔勒环保科技有限公司 | Biomass fuel and technological process for processing the biomass fuel |
| CN102766494A (en) * | 2012-08-09 | 2012-11-07 | 泰安市良达新能源有限责任公司 | Process for preparing coal water slurry by winery wastewater |
| CN104946325B (en) * | 2015-06-15 | 2016-08-17 | 中国寰球工程公司辽宁分公司 | A kind of mud waste water Jiao's slurry and preparation method thereof |
| CN106635207A (en) * | 2017-01-16 | 2017-05-10 | 河北商源科技有限公司 | Semi-coke liquor and production process thereof |
| CN109897704A (en) * | 2017-12-11 | 2019-06-18 | 神华集团有限责任公司 | The preparation method of slurries additive agent and combinations thereof and water-coal-slurry |
| CN113336216A (en) * | 2021-06-29 | 2021-09-03 | 上海臻衍生物科技有限公司 | Catalytic desulfurization method in petroleum coke calcining furnace |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114540088A (en) * | 2022-01-06 | 2022-05-27 | 浙江石油化工有限公司 | Method for producing high-sulfur petroleum coke slurry additive |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59100191A (en) * | 1982-11-30 | 1984-06-09 | Ube Ind Ltd | Preparation of aqueous slurry of solid fuel |
| JPS6088092A (en) * | 1983-10-20 | 1985-05-17 | Ube Ind Ltd | Production of solid fuel/water slurry |
| CN1021343C (en) * | 1986-12-26 | 1993-06-23 | 宇部兴产株式会社 | Solid fuel-water slurry composition and process for preparation of same |
| CN1054394C (en) * | 1997-04-09 | 2000-07-12 | 中国石油化工总公司 | Preparation process of water fluid fuel with solid carbon |
| CN1138847C (en) * | 1999-12-06 | 2004-02-18 | 化学工业部西北化工研究院 | Humic acid additives for water-coal slurry and its preparing process |
| CN1482218A (en) * | 2003-04-18 | 2004-03-17 | 朱复东 | Solid coal water mixture |
-
2006
- 2006-04-24 CN CNB2006100351431A patent/CN100556996C/en active Active
-
2007
- 2007-04-23 WO PCT/CN2007/001318 patent/WO2007124681A1/en active Application Filing
-
2008
- 2008-10-24 MY MYPI20084261A patent/MY157996A/en unknown
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101225335B (en) * | 2008-01-27 | 2011-06-22 | 中国石油化工集团公司 | Preparation method of water coke slurry for gasification |
| CN102268306A (en) * | 2010-06-02 | 2011-12-07 | 深圳市赛尔勒环保科技有限公司 | Biomass fuel and technological process for processing the biomass fuel |
| CN102766494A (en) * | 2012-08-09 | 2012-11-07 | 泰安市良达新能源有限责任公司 | Process for preparing coal water slurry by winery wastewater |
| CN102766494B (en) * | 2012-08-09 | 2016-05-25 | 泰安市良达新能源有限责任公司 | Brewing wastewater is prepared the technique of water-coal-slurry |
| CN104946325B (en) * | 2015-06-15 | 2016-08-17 | 中国寰球工程公司辽宁分公司 | A kind of mud waste water Jiao's slurry and preparation method thereof |
| CN106635207A (en) * | 2017-01-16 | 2017-05-10 | 河北商源科技有限公司 | Semi-coke liquor and production process thereof |
| CN109897704A (en) * | 2017-12-11 | 2019-06-18 | 神华集团有限责任公司 | The preparation method of slurries additive agent and combinations thereof and water-coal-slurry |
| CN109897704B (en) * | 2017-12-11 | 2021-03-09 | 神华集团有限责任公司 | Coal water slurry additive, composition thereof and preparation method of coal water slurry |
| CN113336216A (en) * | 2021-06-29 | 2021-09-03 | 上海臻衍生物科技有限公司 | Catalytic desulfurization method in petroleum coke calcining furnace |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2007124681A1 (en) | 2007-11-08 |
| MY157996A (en) | 2016-08-30 |
| CN100556996C (en) | 2009-11-04 |
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