Shale gas exploitation fracturing propping agents and preparation method thereof
Technical field
The present invention relates to a kind of shale gas exploitation fracturing propping agents, the preparation side of the fracturing propping agents is also related to
Method, belongs to gas production (oil) auxiliary agent technical field.
Background technology
Shale gas is a kind of unconventional gas resource, be with mode preservation of adsorbing and dissociate in shale and mudstone stratum and
Natural gas in its interlayer, main component is methane.Shale gas is often distributed in that thickness in basin is larger, widespread shale hydrocarbon source
In rock stratum.Compared with conventional gas, the features such as shale gas has production life of well length, the production cycle is long, and universal air content
Height, this enable shale gas well it is long-term with stable speed aerogenesis.China's shale gas resource very abundant, is provided according to a preliminary estimate
Source amount is up to 100 tcms, equivalent to twice of conventional gas amount.Shale gas exploitation is to promoting China's energy resource structure to adjust
Whole to have strategic importance, the shale gas of cleaning low-carbon can increase natural gas supply, and Optimization of Energy Structure alleviates emission reduction.
Shale gas once realizes that scale is exploited, and industry especially equipment manufacture can be pulled to develop with engineering services industry, had
Beneficial to tapping new sources of economic growth.
However, the pool forming rules of shale gas, reservoir space, Percolation Law etc. are different from conventional natural gas, particularly store up
Layer has low hole characteristic and the saturating rate of extremely low hypothallus.Therefore, the exploitation difficulty of shale gas is larger, and gas-flow resistance is apparently higher than normal
The natural gas of rule, master recovery efficiency depends on effective fracturing methods.At present, domestic shale gas exploitation technology mainly includes water
Horizontal well multistage fracturing technique, riverfrac treatment technology, multiple fracturing technique and synchronous fracturing technique.And above-mentioned new fracturing technique pair
The performance of fracturing propping agents proposes higher requirement.
Must possess enough passages in shale gas exploitation, in rock can just make gas flow into pit shaft and produce to ground.But
It is that shale gas reservoir is easy to close under high clossing pressure in fine and close aggregation, the crack of fracturing fluid formation.Therefore, prop up
The split harvesting collection shale gas of flow conductivity that the space of support shale keeps good under high clossing pressure is most important.Shale gas is opened
Adopt in pressure break, preferable proppant will can meet following performance:(1) preferable sphericity, to improve flow conductivity;(2) it is high anti-
Compressive Strength, it is ensured that crack is not closed under high clossing pressure;(3) relatively low bulk density and apparent density, to adapt to aquation pressure break
And fractured horizontal well technology;(4) good chemical stability, to adapt to the chemical geological conditions that shale gas reservoir is changeable.
At present, it is in shale gas exploitation to use quartz sand and low-density ceramsite as fracturing propping agents more.General quartz sand
Compression strength is 35MPa, percentage of damage≤10%, and the compression strength of low-density ceramsite is 52MPa, and percentage of damage≤9%, 69Mpa is broken
Broken rate≤20%.However, the clossing pressure of deep layer shale is up to 100Mpa, common quartz sand and haydite is difficult to reach shale gas
Exploitation is required.In addition, haydite materials mainly uses bauxite, production cost is high, and resource is gradually rare, and aluminium is utilized on a large scale
Alumina, which prepares haydite, is used for the restriction that shale gas exploitation receives bauxite resource.Publication No. CN104293337A patent of invention is public
A kind of shale gas special haydite is opened, its raw material is made up of major constituent and extraneous component, major constituent and its mass percent are:Gently
Burning bauxite 50~80%, denaturation clay 3~5%, feldspar 2~12%, coal dust ash 10~30%, extraneous component is bonding agent,
Its addition is the 1~3% of major constituent gross mass, and the haydite is mainly using the aluminium containing aluminium 56.7~59.2% (mass percent)
Alumina, the bulk density of the mesh of haydite 40/70 is 1.30~1.33g/cm3, apparent density is that 2.62~2.63,69MPa percentages of damage are
5.67~8.12%, acid solubility is 4.84~5.3%, and its anti-pressure ability and acid solubility need to be improved.
The content of the invention
Anti-pressure ability of the invention for fracturing propping agents used in the exploitation of current shale gas is weak, percentage of damage is high, acid is molten
There is provided a kind of high intensity, the fracturing propping agents of low acid solubility for the high defects of Xie Du.
Meanwhile, the present invention also provides a kind of preparation method of above-mentioned shale gas exploitation fracturing propping agents.
In order to realize the above object the technical solution adopted in the present invention is:
Shale gas exploitation fracturing propping agents, raw material is made up of the component of following weight/mass percentage composition:Bauxite 43~
55%, shale 43~55%, barium carbonate 1~3%, boric acid 1~2%.
It is preferred that, shale gas exploitation fracturing propping agents, raw material is made up of the component of following weight/mass percentage composition:Bauxite
46~53%, shale 45~51%, barium carbonate 1~2%, boric acid 1~2%.
It is furthermore preferred that shale gas exploitation fracturing propping agents, raw material is made up of the component of following weight/mass percentage composition:Aluminium alum
Soil 47%, shale 50%, barium carbonate 2%, boric acid 1%.
Based on reducing the consideration of cost, the low-grade bauxite that described preferred this area of bauxite is generally defined, wherein
Al2O3Content is 50~60%, SiO2Content is 15~30%.The shale is the shale that this area is generally defined, wherein Al2O3
Content is 15~25%, SiO2Content is 35~50%.
The preparation method of shale gas exploitation fracturing propping agents, comprises the following steps:
(1) fine powder is worn into after respectively crushing bauxite and shale;
(2) each component is accurately taken according to weight/mass percentage composition, mixed, semi-finished product of pelletizing to obtain;
(3) semi-finished product drying, roasting are taken, cooling is produced.
Bauxite and shale fine powder can cross 400 mesh sieves in the step (1).The two first can be crushed to respectively 7mm with
Under (or 2~7mm), then be respectively put into Φ 500mm ball milling and be milled 5~8 hours, the fineness to powder respectively reaches 400 mesh sieves
Remaining≤5%.
Granulation can use routine techniques in the step (2), such as add mixed powder in granulator, spray into the same of water smoke
When keep granulator low speed rotation (rotating speed is 25r/min), be allowed to produce tiny kernel, kernel sieved through 100 eye mesh screens
" introduction " is obtained afterwards, " introduction " is continuously added in granulator, water smoke is constantly sprayed into and feeds mixed powder, low speed rotation (turns
Speed is 25r/min) 1~2 hour produce needed for particle diameter semi-finished product.
It is preferred that, granulation uses High Shear Mixer Granulator method, i.e., first by mixed powder and water addition granulator, (granulator is by turning
Son, rotating cylinder and variable frequency drive motors composition) in, in rotor, rotation (rotating speed is 3500r/min), rotating cylinder low speed rotation (turn at a high speed
Speed is 500r/min) under the conditions of, occur small nucleus in powder, by the dry mixed powder of repeatedly supply, quickly form institute
Need the particle (i.e. semi-finished product) of particle size.Wherein, what is added water in pelletization act as auxiliary granulation, produces mixed powder
Certain viscosity is consequently facilitating coat, but almost all is evaporated at high temperature with moisture in baking operation in follow-up drying.On
Granulation (experiment) machine for stating method of granulating use is purchased from Henan Zheng Kuang machines Co., Ltd, model ZKZL (T) 15.
Need to obtain semi-finished product using the sieved through sieve of 35~65 mesh after pelletizing in the step (2).
Sintering temperature is 1200~1300 DEG C in the step (3), and roasting time is at least 6 hours.It is preferred that, roasting temperature
Spend for 1200~1250 DEG C, roasting time is 6~8 hours.
Need to obtain finished product using the sieved through sieve of 40~70 mesh after cooling down in the step (3).
Beneficial effects of the present invention:
The mechanism of action of each raw material components of fracturing propping agents is in the present invention:Al in bauxite and shale2O3、SiO2
The high strength mullite crystalline phase that high-temperature calcination is produced at 1200~1300 DEG C can improve the compression strength of proppant;BaCO3Make
It is that fluxing agent and bonding agent are added, to reduce sintering temperature, prevents from bonding, while promoting Al2O3、SiO2Generate certain measurer
There is the monocline baryta fledspar of good acid resistance, in proppant surface formation layer protecting film, proppant is protected from rock stratum acid
The corrosion of property and salt alkaloid substance;Boric acid can reduce sintering temperature, by extending sintering time, and baryta fledspar fused mass can be made slow
Mullite in cladding growth, ensures that idiosome has certain porosity, so as to increase proppant while diaphragm is formed
Compressive resistance, in addition, boric acid itself acid resistance improve proppant corrosion resistance, moreover it is possible to reduce K in raw material2O、Na2O
Deng the adverse effect molten to acid.
Fracturing propping agents require detection, the body of 40/70 mesh fracturing propping agents according to SY/T5108-2006 standards in the present invention
Product density is 1.35~1.55g/cm3, apparent density is 2.40~2.75g/cm3, the percentage of damage point under 69Mpa, 86Mpa pressure
Not Wei 2.0~2.9%, 5.0~6.2%, fully meet shale gas exploitation requirement, and density be far below professional standard.Meanwhile, pressure
Split that proppant surface finish is good, sphericity is high, flow conductivity is significantly lifted, and its low-density is conducive to fracturing fluid to pump, and is applicable
Riverfrac treatment and fractured horizontal well technology are developed in shale gas.
Shale gas exploitation is primary raw material with the preferred low-grade bauxite of fracturing propping agents in the present invention, can be greatly reduced
Proppant production cost, breaks away from its dependence to high-grade bauxite, solves the problems, such as comprehensive utilization of resources, with preferable economy
And social benefit.Meanwhile, the auxiliary material of addition can improve the decay resistances such as the compression strength and antiacid alkali of proppant.
The preparation process of shale gas exploitation fracturing propping agents is brief in the present invention, and raw material are taken conveniently, technological parameter
It is controllable, shale gas exploitation pressure break cost can be effectively reduced, suitable for large-scale industrial production.
Brief description of the drawings
Fig. 1 is the microstructure figure that the embodiment of the present invention 1 prepares proppant.
Embodiment
Following embodiments are only described in further detail to the present invention, but do not constitute any limitation of the invention.
Embodiment 1
Shale gas exploitation fracturing propping agents in the present embodiment, raw material is made up of the component of following weight/mass percentage composition:It is low
Grade bauxite 49%, shale 48%, barium carbonate 2%, boric acid 1%.
The preparation method of shale gas exploitation fracturing propping agents, comprises the following steps in the present embodiment:
(1) low-grade bauxite and shale are broken into (i.e. jaw crusher) by experiment Hubei Province respectively and is crushed to below 7mm, then
The ball milling for being separately added into Φ 500mm is milled 6 hours, and the fineness to powder respectively reaches 400 mesh screen residue≤5%;
(2) in terms of weight/mass percentage composition, match somebody with somebody according to low-grade bauxite 49%, shale 48%, barium carbonate 2%, boric acid 1%
Mixed powder processed, first weighs 1.5kg mixed powders and adds in granulator, add water 230g, and regulation rotating cylinder rotating speed is 500r/min, is turned
Rotor speed is 3500r/min, then divides 4 times and add dry mixed powder, and 100g is added every time, is polished 2 minutes, then with 35 mesh, 65
Eye mesh screen sieves to obtain semi-finished product;
(3) take semi-finished product to dry, then be calcined 6 hours at 1230 DEG C, room temperature is cooled to, using 40 mesh, 70 mesh sieve mesh screens
Divide and get product.
The microstructure figure that the present embodiment prepares fracturing propping agents is shown in Fig. 1, is not difficult to find out from figure, fracturing propping agents surface
Preferably, sphericity is high for finish, and particle is homogeneous (its particle diameter is in 40~70 mesh scopes).
Performance detection, testing result are carried out to fracturing propping agents manufactured in the present embodiment according to SY/T5108-2006 standards
It see the table below 1.
Embodiment 2
Shale gas exploitation fracturing propping agents in the present embodiment, raw material is made up of the component of following weight/mass percentage composition:It is low
Grade bauxite 46%, shale 51%, barium carbonate 1%, boric acid 2%.
The preparation method of shale gas exploitation fracturing propping agents, comprises the following steps in the present embodiment:
(1) low-grade bauxite and shale are crushed to below 7mm by Hubei Province respectively, then are separately added into Φ 500mm's
Ball milling is milled 6 hours, and the fineness to powder respectively reaches 400 mesh screen residue≤5%;
(2) in terms of weight/mass percentage composition, match somebody with somebody according to low-grade bauxite 46%, shale 51%, barium carbonate 1%, boric acid 2%
Mixed powder processed, first weighs 1.5kg mixed powders and adds in granulator, add water 230g, and regulation rotating cylinder rotating speed is 500r/min, is turned
Rotor speed is 3500r/min, then divides 4 times and add dry mixed powder, and 100g is added every time, is polished 2 minutes, then with 35 mesh, 65
Eye mesh screen sieves to obtain semi-finished product;
(3) take semi-finished product to dry, then be calcined 8 hours at 1210 DEG C, room temperature is cooled to, using 40 mesh, 70 mesh sieve mesh screens
Divide and get product.
Performance detection, testing result are carried out to fracturing propping agents manufactured in the present embodiment according to SY/T5108-2006 standards
It see the table below 1.
Embodiment 3
Shale gas exploitation fracturing propping agents in the present embodiment, raw material is made up of the component of following weight/mass percentage composition:It is low
Grade bauxite 47%, shale 50%, barium carbonate 2%, boric acid 1%.
Wherein, low-grade bauxite uses the low-grade bauxite on Henan Gongyi periphery, its Al2O3Content is 50~60%,
SiO2Content is 15~30%, and alumina silica ratio is relatively low.The siliceous shale on quarrying shale Henan Gongyi periphery, its Al2O3Content be 15~
25%, SiO2Content is 35~50%, Fe2O3Content be 2~5%, Polodyakonov coefficient coefficient be 1.5~3.5, plasticity index be 5~
20。
The preparation method of shale gas exploitation fracturing propping agents, comprises the following steps in the present embodiment:
(1) low-grade bauxite and shale are crushed to below 7mm by Hubei Province respectively, then are separately added into Φ 500mm's
Ball milling is milled 6 hours, and the fineness to powder respectively reaches 400 mesh screen residue≤5%;
(2) in terms of weight/mass percentage composition, match somebody with somebody according to low-grade bauxite 47%, shale 50%, barium carbonate 2%, boric acid 1%
Mixed powder processed, first weighs 1.5kg mixed powders and adds in granulator, add water 230g, and regulation rotating cylinder rotating speed is 500r/min, is turned
Rotor speed is 3500r/min, then divides 4 times and add dry mixed powder, and 100g is added every time, is polished 2 minutes, then with 35 mesh, 65
Eye mesh screen sieves to obtain semi-finished product;
(3) take semi-finished product to dry, then be calcined 7 hours at 1250 DEG C, room temperature is cooled to, using 40 mesh, 70 mesh sieve mesh screens
Divide and get product.
Performance detection, testing result are carried out to fracturing propping agents manufactured in the present embodiment according to SY/T5108-2006 standards
It see the table below 1.
Embodiment 4
Shale gas exploitation fracturing propping agents in the present embodiment, raw material is made up of the component of following weight/mass percentage composition:It is low
Grade bauxite 46%, shale 50%, barium carbonate 2%, boric acid 2%.
The preparation method of shale gas exploitation fracturing propping agents, comprises the following steps in the present embodiment:
(1) low-grade bauxite and shale are crushed to below 7mm by Hubei Province respectively, then are separately added into Φ 500mm's
Ball milling is milled 6 hours, and the fineness to powder respectively reaches 400 mesh screen residue≤5%;
(2) in terms of weight/mass percentage composition, match somebody with somebody according to low-grade bauxite 46%, shale 50%, barium carbonate 2%, boric acid 2%
Mixed powder processed, first weighs 1.5kg mixed powders and adds in granulator, add water 230g, and regulation rotating cylinder rotating speed is 500r/min, is turned
Rotor speed is 3500r/min, then divides 4 times and add dry mixed powder, and 100g is added every time, is polished 2 minutes, then with 35 mesh, 65
Eye mesh screen sieves to obtain semi-finished product;
(3) take semi-finished product to dry, then be calcined 7 hours at 1240 DEG C, room temperature is cooled to, using 40 mesh, 70 mesh sieve mesh screens
Divide and get product.
Performance detection, testing result are carried out to fracturing propping agents manufactured in the present embodiment according to SY/T5108-2006 standards
It see the table below 1.
Embodiment 5
Shale gas exploitation fracturing propping agents in the present embodiment, raw material is made up of the component of following weight/mass percentage composition:It is low
Grade bauxite 50%, shale 45%, barium carbonate 3%, boric acid 2%.
The basic be the same as Example 2 of the preparation method of shale gas exploitation fracturing propping agents in the present embodiment, except that roasting
It is 1300 DEG C to burn temperature.
Performance detection, testing result are carried out to fracturing propping agents manufactured in the present embodiment according to SY/T5108-2006 standards
It see the table below 1.
Embodiment 6
Shale gas exploitation fracturing propping agents in the present embodiment, raw material is made up of the component of following weight/mass percentage composition:It is low
Grade bauxite 45%, shale 53%, barium carbonate 1%, boric acid 1%.
Wherein, low-grade bauxite is using the low-grade bauxite in Xiaoyi, Shanxi place, its Al2O3Content is 51~59%,
SiO2Content is 20~25%.The shale of quarrying shale Hui nationality, its Al2O3Content is 15~23%, SiO2Content be 35~
45%.
The preparation method be the same as Example 3 of shale gas exploitation fracturing propping agents in the present embodiment.
Performance detection, testing result are carried out to fracturing propping agents manufactured in the present embodiment according to SY/T5108-2006 standards
It see the table below 1.
Embodiment 7
Shale gas exploitation fracturing propping agents in the present embodiment, raw material is made up of the component of following weight/mass percentage composition:It is high
Grade bauxite 43%, shale 54%, barium carbonate 2%, boric acid 1%.
Wherein, Al in high-grade bauxite2O3Content is 60~70%, SiO2Content is 10~15%.
The preparation method be the same as Example 4 of shale gas exploitation fracturing propping agents in the present embodiment.
Performance detection, testing result are carried out to fracturing propping agents manufactured in the present embodiment according to SY/T5108-2006 standards
It see the table below 1.
Embodiment 8
Shale gas exploitation fracturing propping agents in the present embodiment, raw material is made up of the component of following weight/mass percentage composition:It is low
Grade bauxite 55%, shale 43%, barium carbonate 1%, boric acid 1%.
The basic be the same as Example 2 of the preparation method of shale gas exploitation fracturing propping agents in the present embodiment.
Embodiment 9
Shale gas exploitation fracturing propping agents in the present embodiment, raw material is made up of the component of following weight/mass percentage composition:It is low
Grade bauxite 53%, shale 45%, barium carbonate 1%, boric acid 1%.
The basic be the same as Example 4 of the preparation method of shale gas exploitation fracturing propping agents in the present embodiment.
Embodiment 10
Shale gas exploitation fracturing propping agents in the present embodiment, raw material is made up of the component of following weight/mass percentage composition:It is low
Grade bauxite 43%, shale 55%, barium carbonate 1%, boric acid 1%.
The basic be the same as Example 3 of the preparation method of shale gas exploitation fracturing propping agents in the present embodiment.
The embodiment of table 1 prepares the performance test results of fracturing propping agents
Performance indications |
Embodiment 1 |
Embodiment 2 |
Embodiment 3 |
Embodiment 4 |
Embodiment 5 |
Embodiment 6 |
Embodiment 7 |
Bulk density (g/cm3) |
1.35 |
1.37 |
1.41 |
1.39 |
1.42 |
1.49 |
1.55 |
Apparent density (g/cm3) |
2.56 |
2.57 |
2.59 |
2.58 |
2.60 |
2.63 |
2.75 |
Circularity |
0.9 |
0.9 |
0.9 |
0.9 |
0.9 |
0.9 |
0.9 |
Sphericity |
0.9 |
0.9 |
0.9 |
0.9 |
0.9 |
0.9 |
0.9 |
Turbidity (FTU) |
63.2 |
59.3 |
66.7 |
53.2 |
63.8 |
46.8 |
53.7 |
Acid solubility (%) |
3.2 |
3.9 |
3.8 |
3.4 |
3.2 |
3.3 |
3.7 |
Percentage of damage/52Mpa (%) |
1.2 |
1.6 |
0.9 |
1.5 |
1.6 |
1.5 |
0.8 |
Percentage of damage/69Mpa (%) |
2.4 |
2.9 |
2.0 |
2.9 |
2.7 |
2.8 |
2.0 |
Percentage of damage/86Mpa (%) |
5.6 |
6.2 |
5.4 |
5.9 |
5.8 |
6.1 |
5.0 |
Percentage of damage/100Mpa (%) |
7.5 |
8.1 |
7.2 |
7.6 |
7.4 |
7.9 |
6.9 |
Be not difficult to find out from table 1, the embodiment of the present invention prepare fracturing propping agents be respectively provided with low bulk density, low apparent density,
The features such as high intensity, low acid solubility, and as clossing pressure rise percentage of damage increase is not obvious, it is adaptable to high closure pressure
Shale air pressure, which splits, under power adopts and ultradeep well natural gas extraction, is conducive to carrying out pressing crack construction and reduces pressure break cost.
The extensive expansion of fast development and aluminum smelting technology industry with refractories industry, the reserves of high-grade bauxite
It is fewer and fewer, and exploit more difficult.How low-grade bauxite is effectively utilized, these resources is turned waste into wealth, it has also become one
Xiang Xin research topic.Simultaneously because the production cost of ceramsite propping agent is too high, to improve the market competitiveness of haydite, it is necessary to seek
A kind of inexpensive raw materials for production are sought, and shale resource is relatively broad and exploitation is relatively easy, and shale is added in haydite production not
Being only capable of reduction production cost can also efficent use of resources.It is not difficult to find out from table 1, embodiment 1~6 utilizes low-grade bauxite and page
Rock is calcined the mullite crystalline phase for producing high intensity under the high temperature conditions, can equally improve the compression strength of fracturing propping agents.
In other embodiments of the invention, key component can also refer to require to take that (component is with matter in table 2 in raw material
Measure percentage composition meter).
Key component is constituted in the fracturing propping agents of table 2
Component/composition |
Al2O3 |
SiO2 |
Fe2O3 |
TiO2 |
MgO |
CaO |
K2O |
Na2O |
BaCO3 |
Low-grade bauxite |
50~60 |
15~30 |
< 5 |
< 5 |
< 2 |
/ |
< 1 |
< 1 |
/ |
Shale |
15~25 |
35~50 |
< 5 |
< 5 |
/ |
< 5 |
/ |
/ |
/ |
Barium carbonate |
/ |
/ |
/ |
/ |
/ |
/ |
/ |
/ |
> 90 |