CN106811250B - A kind of water coal coke slurry and preparation method thereof - Google Patents
A kind of water coal coke slurry and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of water coal coke slurries, the water coal coke slurry contains petroleum coke powder, low order coal dust, dispersing agent and water, on the basis of water coal coke slurry total weight, petroleum coke powder content is 10-35 weight %, low order coal dust content is 30-60 weight %, and dispersant is 0.1-1 weight %, and water content is 25-40 weight %, the dispersing agent is naphthalene sulfonate and/or humate, and the petroleum coke powder average grain diameter is less than the low order coal dust average grain diameter.The concentration of water coal coke slurry produced by the present invention can achieve 70% or more, apparent viscosity is not higher than 1200mPa.s, rheological characteristic and mobility are preferable, and do not occur within 7 days precipitating firmly, stability is also preferable, therefore, water coal coke slurry produced by the present invention is easy to store, conveys and be atomized, and meets the requirement of gasified raw material.
Description
Technical field
The present invention relates to chemical raw material technical fields, and in particular, to a kind of water coal coke slurry and preparation method thereof and should
The water coal coke slurry of method preparation.
Background technique
Petroleum coke is using various residual oil, pitch or heavy oil as the oil product of the delayed coking production of raw material.With the world
The in poor quality and heaviness of crude quality, oil refining byproduct petroleum coke sulfur content is significantly raised, leads to downstream industry product quality
Decline, the production cost increases, while discharging a large amount of SO2Tail gas seriously pollutes environment, it is difficult to be applied to charcoal element and silicon smelting industry
Etc. traditional fields so that excess phenomenon occurs in petroleum coke, the reasonable of petroleum coke especially high sulfur petroleum coke is looked forward to using becoming petrochemical industry
One of the problem of industry urgent need to resolve.
It is to solve high sulfur petroleum coke surplus, realize high sulfur petroleum coke cleaning that petroleum coke part Substitute coal, which is used as gasified raw material,
The most promising direction utilized.Petroleum coke content is high, calorific value is high, but volatile matter is low, and reactivity is poor, particles hydrophobic
By force, it is difficult to prepare high concentration and the simultaneously good water coke slurry for gasification of stability.Patent application CN101225335A discloses one kind
Water coke slurry for gasification and preparation method thereof, slurry concentration is high, but long-time stability are poor.
In addition, low-order coal such as lignite and jet coal, degree of coalification is low, and volatile matter is high, and reactivity is strong, and pole is rich in particle
Property functional group, so being slurried, stability is good, but be generally difficult to preparation high concentration low-viscosity slurry.Patent CN102181314A is public
A kind of waste water coal coke slurry and preparation method thereof is opened, using a wet-milling pulping process, slurry concentration is not high, and water coal coke slurry is stablized
Property is poor.
Therefore, it is badly in need of a kind of preparation method that can be improved water coal coke slurry concentration and stability now.
Summary of the invention
The purpose of the invention is to overcome the defect that water coal coke slurry concentration is not high and unstable in the prior art, one is provided
Kind water coal coke slurry and preparation method thereof.
Therefore, to achieve the goals above, on the one hand, the present invention provides a kind of water coal coke slurry, which contains
Petroleum coke powder, low order coal dust, dispersing agent and water, on the basis of water coal coke slurry total weight, petroleum coke powder content is 10-35 weight
% is measured, low order coal dust content is 30-60 weight %, and dispersant is 0.1-1 weight %, and water content is 25-40 weight %, institute
Stating dispersing agent is naphthalene sulfonate and/or humate, and the petroleum coke powder average grain diameter is less than the low order coal dust average grain diameter.
Second aspect, the present invention provides a kind of preparation methods of water coal coke slurry, this method comprises:
(1) petroleum coke powder is broken to average grain diameter less than 3mm, water coke slurry is then ground into water, dispersant；
(2) low-order coal is crushed to average grain diameter less than 3mm, is then ground into water-coal-slurry with water, dispersant；
(3) the water coke slurry that step (1) obtains and the water-coal-slurry that step (2) obtain are mixed, wherein the dispersing agent is naphthalene
Sulfonate and/or humate, water coke slurry in petroleum coke powder average grain diameter be less than water-coal-slurry in low order coal dust average grain diameter,
In step (1), the weight ratio of petroleum coke powder, dispersing agent and water is 1:0.001-0.015:0.35-0.6；In step (2), low order
The weight ratio of coal dust, dispersing agent and water is 1:0.001-0.015:0.35-0.6, and the weight of petroleum coke powder and low order coal dust is 1-
3:1-6.
The third aspect, the present invention provides the water coal coke slurries of above method preparation.
In the present invention, petroleum coke and low-order coal hybrid optimization grain composition are prepared into gasification water coal coke slurry, on the one hand, stone
Subparticle, which is made, in oil coke improves the feature of reactivity difference, forms interstitital texture with low-order coal coarse granule, utilizes petroleum coke
Complementarity on high carbon content and the physico-chemical properties such as low activity and low-order coal high stability high activity, overcomes water-coal-slurry and water is burnt
Starch stability difference and the low disadvantage of single gradation water coal coke slurry slurry slurry concentration.On the other hand, having for gasification slurry is improved
Component is imitated, petroleum coke utilization ways has been opened up, has realized the green clean utilization of petroleum coke.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
On the one hand, the present invention provides a kind of water coal coke slurry, which contains petroleum coke powder, low order coal dust, dispersion
Agent and water, on the basis of water coal coke slurry total weight, petroleum coke powder content is 10-35 weight %, and low order coal dust content is 30-60 weight
% is measured, dispersant is 0.1-1 weight %, and water content is 25-40 weight %, and the dispersing agent is naphthalene sulfonate and/or corruption
Hydrochlorate is grown, the petroleum coke powder average grain diameter is less than the low order coal dust average grain diameter.
Water coal coke slurry according to the present invention, it is preferable that on the basis of water coal coke slurry total weight, petroleum coke powder content is
20-35 weight %, low order coal dust content are 35-50 weight %, and dispersant is 0.1-0.5 weight %, water content 25-30
Weight %.
In the present invention, the petroleum coke be using various residual oil, pitch or heavy oil as the green coke of the delayed coking production of raw material,
It, which fixes carbon content, can be greater than 88%, and Hardgrove grind ability index can be greater than 40, and sulfur content can be 4-7%.
In the present invention, the low-order coal is the low-order coal type of this field routine, such as can be jet coal, not glue
At least one of coal, weakly caking coal and lignite.
Water coal coke slurry according to the present invention, as long as the petroleum coke powder average grain diameter is average less than the low order coal dust
Partial size, it is preferable that the low order coal dust average grain diameter is 1.5-5 times of the petroleum coke powder average grain diameter, it is highly preferred that
The petroleum coke powder average grain diameter is 25-35 μm, and the low order coal dust average grain diameter is 70-95 μm, so as to improve water
Its stability is improved while the concentration of coal coke slurry.
Water coal coke slurry according to the present invention, it is preferable that the dispersing agent is the mixing of naphthalene sulfonate and humate
The weight ratio of object, naphthalene sulfonate and humate is 6:3-4, so as to improve it while improving the concentration of water coal coke slurry
Stability.
In the present invention, naphthalene sulfonate can at least one of for sodium naphthalene sulfonate, naphthalene sulfonic acids calcium and poly- naphthalene formaldehyde sulfonate,
Preferably sodium naphthalene sulfonate and/or naphthalene sulfonic acids calcium, humate can be sodium humate, calcium humate, potassium humate and humic acid
At least one of magnesium, preferably sodium humate and/or calcium humate.
Second aspect, the present invention also provides a kind of preparation methods of water coal coke slurry, this method comprises:
(1) petroleum coke powder is broken to average grain diameter less than 3mm, water coke slurry is then ground into water, dispersant；
(2) low-order coal is crushed to average grain diameter less than 3mm, is then ground into water-coal-slurry with water, dispersant；
(3) the water coke slurry that step (1) obtains and the water-coal-slurry that step (2) obtain are mixed, wherein the dispersing agent is naphthalene
Sulfonate and/or humate, water coke slurry in petroleum coke powder average grain diameter be less than water-coal-slurry in low order coal dust average grain diameter,
In step (1), the weight ratio of petroleum coke powder, dispersing agent and water is 1:0.001-0.015:0.35-0.6；In step (2), low order
The weight ratio of coal dust, dispersing agent and water is 1:0.001-0.015:0.35-0.6, and the weight of petroleum coke powder and low order coal dust is 1-
3:1-6.
Method according to the present invention, it is preferable that in step (1), the weight ratio of petroleum coke powder, dispersing agent and water is 1:
0.005-0.01:0.4-0.5；In step (2), the weight ratio of low order coal dust, dispersing agent and water is 1:0.005-0.01:0.4-
0.5, the weight of petroleum coke powder and low order coal dust is 1-2:1-3.
Method according to the present invention, as long as the petroleum coke powder average grain diameter in water coke slurry is less than low-order coal in water-coal-slurry
Powder average grain diameter, it is preferable that the low order coal dust average grain diameter in water-coal-slurry is the petroleum coke powder average grain diameter in water coke slurry
1.5-5 times, it is highly preferred that the petroleum coke powder average grain diameter in water coke slurry is 25-35 μm, the low order coal dust in water-coal-slurry is average
Partial size is 70-95 μm, so as to improve its stability while improving the concentration of water coal coke slurry.
Method according to the present invention, it is preferable that the dispersing agent is the mixture of naphthalene sulfonate and humate, naphthalene
The weight ratio of sulfonate and humate is 6:3-4, so as to improve its stabilization while improving the concentration of water coal coke slurry
Property.
Method according to the present invention, in step (1), petroleum coke powder is broken to method of the average grain diameter less than 3mm can
Think ball mill grinding, wherein this method can also include: petroleum coke powder be broken to average grain diameter less than before 3mm by petroleum coke elder generation
It is crushed to 8-10mm.
Method according to the present invention, in step (2), low-order coal is crushed to method of the average grain diameter less than 3mm can
Think ball mill grinding, wherein this method can also include: low-order coal be crushed to average grain diameter less than before 3mm by low-order coal elder generation
It is crushed to 8-10mm.
The third aspect, the present invention also provides the water coal coke slurries of above method preparation.
The concentration of water coal coke slurry produced by the present invention can achieve 70% or more, and apparent viscosity is not higher than 1200mPa.s, stream
Denaturation and mobility are preferable, and do not occur within 7 days precipitating firmly, and stability is also preferable, therefore, water coal coke slurry produced by the present invention
It is easy to store, conveys and be atomized, meets the requirement of gasified raw material.
Embodiment 1
The present embodiment is for illustrating water coal coke slurry and preparation method thereof of the invention.
(1) 25g petroleum coke is first crushed to 10mm, then by itself and 10g water, 0.2g dispersing agent (sodium naphthalene sulfonate and corruption
Growing sour sodium weight, mixing and ball milling is starched at water coke in the ball mill for 6:4)；
(2) 45g low-order coal (jet coal) is first crushed to 10mm, then in the ball mill with 19.5g water, 0.3g dispersing agent
Mixing and ball milling is at water-coal-slurry；
(3) the water coke slurry that step (1) obtains and the water-coal-slurry that step (2) obtain are mixed, the petroleum coke powder in water coke slurry
Average grain diameter is 25 μm, and the low order coal dust average grain diameter in water-coal-slurry is 70 μm,
Wherein, on the basis of water coal coke slurry total weight obtained, petroleum coke powder content is 25 weight %, low order coal dust content
For 45 weight %, dispersant is 0.5 weight %, and water content is 29.5 weight %.
Embodiment 2
The present embodiment is for illustrating water coal coke slurry and preparation method thereof of the invention.
(1) 10g petroleum coke is first crushed to 8mm, then by itself and 5g water, 0.04g dispersing agent (naphthalene sulfonic acids calcium and humic
The weight of sour calcium for 6:4), starch at water coke in the ball mill by mixing and ball milling；
(2) 60g low-order coal (lignite) is first crushed to 10mm, then in the ball mill with 24.9g water, 0.06g dispersing agent
Mixing and ball milling is at water-coal-slurry；
(3) the water coke slurry that step (1) obtains and the water-coal-slurry that step (2) obtain are mixed, the petroleum coke powder in water coke slurry
Average grain diameter is 30 μm, and the low order coal dust average grain diameter in water-coal-slurry is 80 μm,
Wherein, on the basis of water coal coke slurry total weight obtained, petroleum coke powder content is 10 weight %, low order coal dust content
For 60 weight %, dispersant is 0.1 weight %, and water content is 29.9 weight %.
Embodiment 3
The present embodiment is for illustrating water coal coke slurry and preparation method thereof of the invention.
(1) 35g petroleum coke is first crushed to 10mm, then by itself and 15g water, 0.5g dispersing agent (sodium naphthalene sulfonate and corruption
Growing the weight of sour sodium, mixing and ball milling is starched at water coke in the ball mill for 6:4)；
(2) 35g low-order coal (lignite) is first crushed to 8mm, then in the ball mill with 14.05g water, 0.45g dispersing agent
Mixing and ball milling is at water-coal-slurry；
(3) the water coke slurry that step (1) obtains and the water-coal-slurry that step (2) obtain are mixed, the petroleum coke powder in water coke slurry
Average grain diameter is 35 μm, and the low order coal dust average grain diameter in water-coal-slurry is 95 μm,
Wherein, on the basis of water coal coke slurry total weight obtained, petroleum coke powder content is 35 weight %, low order coal dust content
For 35 weight %, dispersant is 0.95 weight %, and water content is 29.05 weight %.
Embodiment 4
The present embodiment is for illustrating water coal coke slurry and preparation method thereof of the invention.
Water coal coke slurry is prepared according to the method for embodiment 1, unlike, the weight of dispersing agent sodium naphthalene sulfonate and sodium humate
Than for 6:7.
Embodiment 5
The present embodiment is for illustrating water coal coke slurry and preparation method thereof of the invention.
Water coal coke slurry is prepared according to the method for embodiment 1, unlike, the weight of dispersing agent sodium naphthalene sulfonate and sodium humate
Than for 6:2.
Embodiment 6
The present embodiment is for illustrating water coal coke slurry and preparation method thereof of the invention.
Water coal coke slurry is prepared according to the method for embodiment 1, unlike, dispersing agent is only sodium naphthalene sulfonate.
Embodiment 7
The present embodiment is for illustrating water coal coke slurry and preparation method thereof of the invention.
Water coal coke slurry is prepared according to the method for embodiment 1, unlike, dispersing agent is only sodium humate.
Comparative example 1
Water coal coke slurry is prepared according to the method for embodiment 1, unlike, dispersing agent is sodium lignin sulfonate.
Test case
The table of water coal coke slurry made from embodiment 1-7 and comparative example 1 is measured using national standard GBT 18856.4-2008 method
Viscosity is seen, the results are shown in Table 1.
Water coal coke slurry made from embodiment 1-7 and comparative example 1 is respectively charged into test tube, observes and in slurry occurs precipitating
Time the results are shown in Table 1 to measure the stability of water coal coke slurry.
Table 1
| Embodiment | Water coal coke slurry concentration (%) | Apparent viscosity (mPa.s) | Stability |
| Embodiment 1 | 70.5 | 1106 | It precipitates within 11st day |
| Embodiment 2 | 70.1 | 1134 | It precipitates within 10th day |
| Embodiment 3 | 70.95 | 1137 | It precipitates within 10th day |
| Embodiment 4 | 70.5 | 1150 | It precipitates within 9th day |
| Embodiment 5 | 70.5 | 1160 | It precipitates within 9th day |
| Embodiment 6 | 70.5 | 1200 | It precipitates within 8th day |
| Embodiment 7 | 70.5 | 1200 | It precipitates within 8th day |
| Comparative example 1 | 66.8 | 1500 | It precipitates within 3rd day |
By embodiment 1-7 as can be seen that the concentration of water coal coke slurry produced by the present invention can achieve compared with comparative example 1
70% or more, apparent viscosity is not higher than 1200mPa.s, and rheological characteristic and mobility are preferable, and do not occur within 7 days precipitating firmly, surely
Qualitative also preferable, therefore, water coal coke slurry produced by the present invention is easy to store, conveys and be atomized, and meets the requirement of gasified raw material.
In the present invention, petroleum coke and low-order coal hybrid optimization grain composition are prepared into gasification water coal coke slurry, on the one hand, stone
Subparticle, which is made, in oil coke improves the feature of reactivity difference, forms interstitital texture with low-order coal coarse granule, utilizes petroleum coke
Complementarity on high carbon content and the physico-chemical properties such as low activity and low-order coal high stability high activity, overcomes water-coal-slurry and water is burnt
Starch stability difference and the low disadvantage of single gradation water coal coke slurry slurry slurry concentration.On the other hand, having for gasification slurry is improved
Component is imitated, petroleum coke utilization ways has been opened up, has realized the green clean utilization of petroleum coke.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (9)
1. a kind of water coal coke slurry, which is characterized in that the water coal coke slurry contains petroleum coke powder, low order coal dust, dispersing agent and water, with water
On the basis of coal coke slurry total weight, petroleum coke powder content is 10-35 weight %, and low order coal dust content is 30-60 weight %, dispersing agent
Content is 0.1-1 weight %, and water content is 25-40 weight %, and the dispersing agent is the mixture of naphthalene sulfonate and humate,
The weight ratio of naphthalene sulfonate and humate is 6:3-4, and the petroleum coke powder average grain diameter is less than the low order coal dust and is averaged grain
Diameter.
2. water coal coke slurry according to claim 1, wherein on the basis of water coal coke slurry total weight, petroleum coke powder content is
20-35 weight %, low order coal dust content are 35-50 weight %, and dispersant is 0.1-0.5 weight %, water content 25-30
Weight %.
3. water coal coke slurry according to claim 1, wherein the low order coal dust average grain diameter is average for the petroleum coke powder
1.5-5 times of partial size.
4. water coal coke slurry according to claim 3, wherein the petroleum coke powder average grain diameter is 25-35 μm, the low order
Coal dust average grain diameter is 70-95 μm.
5. a kind of preparation method of water coal coke slurry, which is characterized in that this method comprises:
(1) petroleum coke powder is broken to average grain diameter less than 3mm, water coke slurry is then ground into water, dispersant；
(2) low-order coal is crushed to average grain diameter less than 3mm, is then ground into water-coal-slurry with water, dispersant；
(3) the water coke slurry that step (1) obtains and the water-coal-slurry that step (2) obtain are mixed, wherein the dispersing agent is naphthalene sulfonic acids
The weight ratio of the mixture of salt and humate, naphthalene sulfonate and humate is 6:3-4, and the petroleum coke powder in water coke slurry is average
Partial size is less than the low order coal dust average grain diameter in water-coal-slurry, and in step (1), the weight ratio of petroleum coke powder, dispersing agent and water is 1:
0.001-0.015:0.35-0.6；In step (2), the weight ratio of low order coal dust, dispersing agent and water is 1:0.001-0.015:
The weight of 0.35-0.6, petroleum coke powder and low order coal dust is 1-3:1-6.
6. according to the method described in claim 5, wherein, in step (1), the weight ratio of petroleum coke powder, dispersing agent and water is 1:
0.005-0.01:0.4-0.5；In step (2), the weight ratio of low order coal dust, dispersing agent and water is 1:0.005-0.01:0.4-
0.5, the weight of petroleum coke powder and low order coal dust is 1-2:1-3.
7. according to the method described in claim 5, wherein, the low order coal dust average grain diameter in water-coal-slurry is the petroleum in water coke slurry
1.5-5 times of coke powder average grain diameter.
8. according to the method described in claim 7, wherein, the petroleum coke powder average grain diameter in water coke slurry is 25-35 μm, water-coal-slurry
In low order coal dust average grain diameter be 70-95 μm.
9. the water coal coke slurry of the preparation of the method according to any one of claim 5-8.
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| CN1275610A (en) * | 1999-05-28 | 2000-12-06 | 中国石油化工集团公司 | Refinery coke modified low-grade coal-water slurry mixture and use thereof |
| CN1275611A (en) * | 1999-05-28 | 2000-12-06 | 中国石油化工集团公司 | Low-grade coal modified refinery coke water slurry composition and use thereof |
| CN101935564A (en) * | 2010-09-08 | 2011-01-05 | 山东科技大学 | Method for manufacturing oil coke water slurry |
| CN102952595A (en) * | 2012-11-20 | 2013-03-06 | 煤炭科学研究总院 | Superfine water coal slurry and preparation method of superfine water coal slurry |
| CN104877721A (en) * | 2015-06-15 | 2015-09-02 | 中国石油大学(华东) | Method for improving stability of water-coke slurry |
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- 2015-11-27 CN CN201510847693.2A patent/CN106811250B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1275610A (en) * | 1999-05-28 | 2000-12-06 | 中国石油化工集团公司 | Refinery coke modified low-grade coal-water slurry mixture and use thereof |
| CN1275611A (en) * | 1999-05-28 | 2000-12-06 | 中国石油化工集团公司 | Low-grade coal modified refinery coke water slurry composition and use thereof |
| CN101935564A (en) * | 2010-09-08 | 2011-01-05 | 山东科技大学 | Method for manufacturing oil coke water slurry |
| CN102952595A (en) * | 2012-11-20 | 2013-03-06 | 煤炭科学研究总院 | Superfine water coal slurry and preparation method of superfine water coal slurry |
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