CN104326763A - Method for using niobium boride ceramic beads for preparation of high temperature high pressure resistant oil well cementation test block - Google Patents
Method for using niobium boride ceramic beads for preparation of high temperature high pressure resistant oil well cementation test block Download PDFInfo
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- CN104326763A CN104326763A CN201410487285.6A CN201410487285A CN104326763A CN 104326763 A CN104326763 A CN 104326763A CN 201410487285 A CN201410487285 A CN 201410487285A CN 104326763 A CN104326763 A CN 104326763A
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Abstract
The present invention provides a method for using niobium boride ceramic beads for preparation of a high temperature high pressure resistant oil well cementation test block, and the method comprises preparing niobium boride closed hollow ceramic beads, dosing, mixing, stirring and mixing pulp, adding into testing moulds, and testing performance, and is characterized in that: in a stirrer, adding 55 ~ 65wt% of G-level oil well cement, 25 ~ 35wt% of the niobium boride closed hollow ceramic beads with the particle size of 10-50 mum, 5 ~ 7wt% of fly ash with the ignition loss of 1.1%, 1.5 ~ 2wt% of calcium oxide with the purity of 99.9%, 0.5 ~ 1.0wt% of sodium sulfate and 1 ~ 3wt% of micro silicon into a stirrer for stirring and mixing the pulp for 40 s according to the water cement ratio of 0.5-0.7 (W / C), pouring into a group of two testing moulds with the length, width and height of 53mm * 53mm * 53mm, curing for 24 hours and 48 hours in a water bath curing box at the constant temperature of 52 DEG C, after demoulding, soaking with cold water for 1 hour, and testing performance indexes.
Description
Technical field
The present invention relates to the method that niobium (Nb) boride ceramic fine bead prepares the test block of high temperature high voltage resistant oil well cementing, belong to field of material technology.
Background technology
Current domestic well cementation light-weight additive adopts the drift pearl in flyash, and comprise heavy pearl and drift pearl at flyash, heavy pearl density is at 1.1 ~ 2.8g/cm
3between, content accounts for flyash 30 ~ 70%, and drift pearl is the glass microballon being less than water-mass density in flyash, and drift pearl mainly comprises aluminosilicate glass microballon and porous carbon granule, drift pearl after removing carbon granule mainly comprises Thin-walled Aluminum silex glass microballon, surfaces externally and internally is smooth, and volume is large, is that one is rounded, light weight, closed pore are hollow, wear-resisting, high temperature resistant, thermal conductivity is little, intensity is high, drift pearl amount accounts for 0.5 ~ 1% of flyash total amount, and aluminosilicate glass microballon is hollow spherosome.
Drift pearl wherein in flyash it be coal dust in thermal power plant boiler when 1100 ~ 1500 ° of C burning, clayey material melts becomes microlayer model, in stove turbulent flow hot air acting under at a high speed spin, form perfectly round sial spheroid, the gases such as nitrogen, hydrogen and carbonic acid gas that burning and scission reaction produce, undergoes rapid expansion in the high temperature aluminum silicon spheroid of melting, under capillary effect, form the glass envelope of hollow, then enter flue to cool rapidly, after sclerosis, become the vitreous state cenosphere of high vacuum, i.e. fly ash float.
Flyash is put into water stir, leave standstill for some time, because drift pearl density is less than water-mass density, will swim in the water surface pulls out and dry, be and float pearl, the drift pearl in flyash is canescence, and main component is SiO
2account for 70% and AI
2o
3account for 13%, loss on ignition is 0.40% ~ 0.574%, density 0.475 ~ 0.574g/cm
3, wall thickness 1.44 ~ 5.41 μm, particle size range is mainly distributed in 147 ~ 84 μm.
In recent years, due to the impact of northern haze weather, the big-and-middle-sized thermal power generation of China adopts the desulfurization technology of environmental protection, not containing in flyash floats pearl, cause in short supply, only have the drift pearl that middle small coal power plants and arcola do not adopt desulfurization technology supply a small amount of, drift the in short supply of pearl causes price increase, and float that pearl is impure is mixed with flyash, affect cementing quality.
In reinforcing oil well field, hydrocarbon distribution is wide, and long shut-in well is more and more, and main use of long shut-in well is high temperature high voltage resistant well cementing of cement, and long shut-in well is main adopts high temperature high voltage resistant test block, wants to make the density of slurries at 0.72 g/cm
3~ 1.5 g/cm
3between, density must at 0.5 g/cm for the lightening material (inorganic mineral material and organic synthesis material composition) of non-drift pearl
3~ 0.7 g/cm
3between, (density of G level oil well watertight is at 3.1 g/cm just to make the slurries of high temperature high voltage resistant
3, light-weight additive density must be less than 1 g/cm
3, just can configure density 1.0 g/cm
3~ 1.5 g/cm
3between slurries, precondition is that light-weight additive addition can not exceed 40% of total amount, otherwise can affect well cementation test block ultimate compression strength).
Different according to the well cementation degree of depth, usually the oil well of less than 2000 meters low hot-well, low temperature oil-well is cemented the well and is used low-pressure low-temperature slurries, and the temperature in oil well is between 70 ~ 90 ° of C, and namely slurries are close at 1.8 g/cm
3~ 1.9 g/cm
3; Be middle hot-well between 2000 ~ 4000 meters, (, between 90 ~ 150 ° of C, namely serum density is at 1.6 g/cm for the temperature in oil well with the slurries of pressure in anti-for middle temperature oil well cementing
3~ 1.7 g/cm
3; And be greater than 4000 meters for hot hole, the slurries of high-temperature oil well well cementation high temperature high voltage resistant, the temperature in oil well is between 150 ~ 240 ° of C, and namely serum density is at 1.0 g/cm
3~ 1.5 g/cm
3.
Because land low temperature oil-well hydrocarbon resources is gradually reducing, progressively by land low temperature oil-well, landwards deep layer and bathypelagic are developed in exploitation, traditional well cementing material drift pearl can not meet the needs of deep layer high-temperature oil well, need to employ new technology, novel process, novel material to be to meet the requirement of deep-level high pressure high-temperature oil well, within 24 hours, pressure is greater than 60Mpa, and serum density is at 1.0 g/cm
3~ 1.5 g/cm
3between, ceramic fine bead resistance to hydrostatic pressure intensity 110 ~ 250Mpa.
Summary of the invention
The object of the invention is to overcome prior art present situation, find out the breach of new technology, there is provided a kind of cost low, excellent property, can replace the pearl of wafing in flyash, excellent property, make density determine velocity of variation and be less than 0.02, reach design density, make niobium (Nb) boride closed pore hollow ceramic microspheres by the method for organic synthesis, density range 0.50 g/cm
3~ 0.85g/cm
3, and then configuration low density 1.0 g/cm
3~ 1.5g/cm
3the preparation method of oil well cementing high temperature high voltage resistant well cementation test block, meets the requirement of long shut-in well well cementing material.
its technical scheme is.
Comprise the preparation of niobium (Nb) boride closed pore hollow ceramic microspheres, batching, mixing, stirring sized mixing, die trial, performance test, niobium (Nb) boride closed pore hollow ceramic microspheres performance test comprise its floatability mensuration, density, resistance to hydrostatic pressure intensity mensuration, serum density mensuration, sedimentation stability, thickening time, fall fluid loss, withstand voltage density test, the liquidity scale, carry out compressive property test.
Comprise the following steps:
Prepared by A, niobium (Nb) boride closed pore hollow ceramic microspheres:
The first step, batching: by particle diameter 1 ~ 10 μm of Niobium Pentxoxide powder, 3 ~ 20 μm of boron carbide powders and, 5 ~ 15 μm of boron oxides are in proportion: wt%:3 ~ 6,70 ~ 80wt%:15 ~ 20 wt%;
Second step, base: by particle diameter 1 ~ 10 μm of Niobium Pentxoxide powder, 3 ~ 20 μm of boron carbide powders and, 5 ~ 15 μm of boron oxides are mixed to get powder mix by the proportional sampling of the first step, by particle diameter 1 ~ 10 μm of Niobium Pentxoxide powder, 3 ~ 20 μm of boron carbide powders and, resol is added in 5 ~ 15 μm of boron oxide powder mixs, ratio is: 1 wt%:0.5 ~ 0.8 wt%, particle diameter 1 ~ 5 μm of Niobium Pentxoxide powder, 5 ~ 20 μm of boron carbide powders and, with resol mixing and stirring in 5 ~ 10 μm of boron oxide powder mixs, solidification treatment at 50 ~ 100 ° of C temperature, cured body is pulverized in powder-making machine, obtain 30 ~ 100 μm of powder mixs, compound puts into mould, pressing machine applies 1 ~ 3 MPa pressure, extrusion molding obtains blank,
3rd step, high-temperature firing: second step is obtained blank and puts into high temperature sintering furnace, under 1600 ~ 2000 ° of C, it is 5 ~ 8 hours in the time of hydrogen atmosphere heat preservation sintering, 300 ~ 500 ° of C carbonization treatment obtain niobium boride powder, and resol is high reactivity carbon source reduction Niobium Pentxoxide is niobium (Nb) boride;
4th step, the making of niobium (Nb) boride solid microbeads: the 3rd step is obtained niobium (Nb) boride block crushing large particle, oarse-grained particle diameter is at 300 ~ 600 μm, be converted into order number at 30 ~ 50mesh, balling machine is processed into the full particle of particle diameter 5 ~ 10 μm of niobium (Nb) boride spherical shape, be processed into solid ball, balling machine is not jaw crusher, jaw crusher utilizes metal accelerating impact or knocks material, the material shapes formed is sheet, many prismatics etc. are irregularly shaped, nodularization processing is that material blows afloat by blower fan, rotary motion phase mutual friction between material is spherical particle, the particle of spherical shape is even in each particle stress distribution, ultimate compression strength is large, sheet, many prismatics high-temperature expansion sintered shape is still original shape, irregular shape is through high-temperature expansion sintering in cuttlefish fish head shapes, and ultimate compression strength is low, grinds stranding one fragmentation with two fingers, the density of broken rear slurry can increase, water cement ratio also increases, and setting time is long, and test block contraction ratio is large, blind hole, flat impossible Cheng Yuan's, nodularization is different with attrition crushing principle, and the performance of microballon is also different,
5th step, niobium (Nb) boride liquid slurry makes: the weight percent of niobium (Nb) boride liquid slurry consists of: particle diameter 5 ~ 10 μm of niobium (Nb) boride 65 ~ 70 wt%: water 30 ~ 35 wt%;
6th step, whipping agent add: to the 5th step make niobium (Nb) boride liquid slurry in add whipping agent, the one in calcium carbonate, potassium sulfate or sodium sulfate, concentration is 1 ~ 3g/L, expanding volume and wall thickness relevant with add-on;
7th step, prepared by niobium (Nb) boride closed pore hollow ceramic microspheres: the 6th step mixed solution is starched abundant agitation and filtration, adopt high pressure spraying high speed centrifugation rotary spraying technique, form microballoon, through overexpansion on the oxygenation gas furnace of zonal control, high temperature sintering, melt surface vitreous, balling-up, the concentration of oxygen is 30 ~ 35%, the concentration of oxygen is higher, burning-point is lower, burn more abundant, the heat of release is more, temperature is higher, wherein expansion temperature 800 ~ 900 ° of C, dry sintering temperature at 1400 ~ 1600 ° of C, melt surface temperature 1700 ~ 1800 ° of C, become bulb temperature 1400 ~ 1500 ° of C, balling-up selects classification to obtain 5 ~ 50 μm of niobium (Nb) boride closed pore hollow ceramic microspheres through Feng Li Cheongju, high-pressure pump is adopted to starch extracting liquid from mixed solution, through pressurization, mixed solution slurry is delivered to centrifugal rotation spraying machine, the rotating speed of high speed centrifugation motor is at 24000 revs/min, motor is high temperature resistant at 1800 ° of C, high speed rotating produces larger centrifugal force and forms microballon, the size of microballon and injection aperture, pressure is relevant with speed, the higher expanding volume of dehydration expansion temperature is larger, relevant with temperature height, melt surface temperature could form niobium (Nb) boride closed pore hollow ceramic microspheres, mineral substance produces activity after the above high temperature sintering of 900 ° of C, easy generation hydration reaction, generate spawn, improve early strength, as unslaked lime, flyash, silica flour etc., in addition, particle diameter is less, specific surface is larger, activity is larger, speed of response is fast, and the composition floating pearl determined by the composition of coal, the size of particle diameter cannot manual control, therefore the drift pearl performance in flyash can not change, i.e. wall thickness, the size of particle diameter and ultimate compression strength can not change, high pressure spraying high speed centrifugation rotary spraying technique can control the size of the particle diameter of microballon, wall thickness and ultimate compression strength, classification is selected to obtain 5 ~ 50 μm of niobium (Nb) boride closed pore hollow ceramic microspheres through Feng Li Cheongju, niobium (Nb) boride closed pore hollow ceramic microspheres wall thickness is at 10 ~ 20 μm, ultimate compression strength is at 110 ~ 250 MPa, and the drift pearl wall thickness in flyash is less than 6 μm, maximum compressive strength 20 Mpa performance index artificially cannot control, relevant with the performance of material own, prepare high temperature resistant, the raw material light-weight additive that high pressure well cementation test block uses, as the performance of hollow glass matter closed pore microballon and various well cementation light-weight additive material, performance index are as wall thickness, density, sphericity, its floatability, ultimate compression strength, opening and closing hole, size, must be artificially controlled, meet These parameters, well cementation light-weight additive wide accommodation, in addition, ceramic material property exceedes alloy material, be widely used in space flight, military project, the fields such as machinery, prepared by the method for synthetic, cost is low, performance is high.
8th step, testing performance index:
A, its floatability measures: take particle diameter 5 ~ 50 μm of niobium (Nb) boride closed pore hollow ceramic microspheres 100 grams, pour in the beaker of 1000 milliliters, pour 500 ml tap waters again into fall in beaker, stir with glass stick, leave standstill 1 hour, niobium (Nb) boride closed pore hollow ceramic microspheres floating in beaker is drift pearl, heavy pearl is precipitated as in beaker bottom, the proportion of heavy pearl is greater than the proportion of water, explanation sintering time is short, sintering temperature is low, take out respectively and dry weigh floating pearl and heavy pearl in beaker, calculate its floatability, the its floatability of niobium (Nb) boride closed pore hollow ceramic microspheres in water should be greater than 98%, the density domination of light-weight additive is in rational density range, i.e. 0.5g/cm
3~ 0.85 g/cm
3between, if the niobium (Nb) boride closed pore hollow ceramic microspheres precipitation that sintering time is short, proportion is greater than water, broken niobium (Nb) boride closed pore hollow ceramic microspheres water suction precipitation,
B, measure the density of niobium (Nb) boride closed pore hollow ceramic microspheres: the volumetric flask getting 100 milliliters is weighed G
1, then niobium (Nb) boride closed pore hollow ceramic microspheres is poured in 100 milliliters of volumetric flasks, the scale marks of niobium (Nb) boride closed pore hollow ceramic microspheres concave surface and 100 milliliters of volumetric flasks is tangent, and weighing niobium (Nb) boride closed pore hollow ceramic microspheres and bottle are heavily G
2, 100 milliliters of niobium (Nb) boride closed pore hollow ceramic microspheres nt wt net weights are G
2-G
1, obtain m=ρ V by quality, density and volume, density p=(G
2-G
1)/V, according to the cementing requirements of high temperature high voltage resistant test block, the density of test block is at 1.0 ~ 1.5g/cm
3, niobium (Nb) boride closed pore hollow ceramic microspheres density should at 0.5g/cm
3~ 0.85 g/cm
3between;
C, the mensuration of resistance to hydrostatic pressure intensity: weigh niobium (Nb) boride closed pore hollow ceramic microspheres 100 grams and pour in hydrostaticpressure intensity test tube, hydrostaticpressure intensity test tube is connected with pressure pump, water in pressure pump is stressed in hydrostaticpressure intensity test tube, record force value, the niobium (Nb) boride closed pore hollow ceramic microspheres stopping pressurization taking out in test tube measures its floatability, after pressurization 110MPa, take out niobium (Nb) boride closed pore hollow ceramic microspheres and measure its floatability, if the niobium (Nb) boride closed pore hollow ceramic microspheres its floatability after pressurization is consistent with uninflated niobium (Nb) boride closed pore hollow ceramic microspheres its floatability, show that the intensity of niobium (Nb) boride closed pore hollow ceramic microspheres resistance to hydrostatic pressure is greater than 110 MPa, use the same method and measure 150MPa, 180 MPa, 200 MPa, the numerical value such as 250MPa, resistance to hydrostatic pressure intensity and niobium (Nb) boride closed pore hollow ceramic microspheres ultimate compression strength, the intensity of niobium (Nb) boride closed pore hollow ceramic microspheres resistance to hydrostatic pressure is at 110 ~ 250MPa, and the maximum hydrostaticpressure intensity that fly ash float detects is 20 MPa, wall thickness is less than 6 μm, particle diameter is greater than 80 μm, the ultimate compression strength of test block depends on the ultimate compression strength of drift pearl, drift pearl in flyash is not suitable for the well cementation of High Temperature High Pressure oil well, namely less than 4000 meters are not suitable for, temperature is greater than the well cementation of the oil well of 150 ° of C, be suitable only for more than 2000 meters, be less than the well cementation of the oil well of 90 ° of C, as everyone knows, stupalith is widely used in space flight, chemical industry, the fields such as machinery, the performance index such as stupalith ultimate compression strength are considerably beyond synthetic metals material, therefore niobium (Nb) boride closed pore hollow ceramic microspheres can be used for the well cementation of High Temperature High Pressure oil well, stupalith is ultimate compression strength in making processes, wall thickness, the human controllable such as particle diameter, other materials is incomparable,
The variable density value of d, detection niobium (Nb) boride closed pore hollow ceramic microspheres: the variable density scope of the niobium (Nb) boride closed pore hollow ceramic microspheres of the sampling spot of same batch of different positions is at ± 0.01 g/cm
3; Namely the density requirements of niobium (Nb) boride closed pore hollow ceramic microspheres of same batch is at 0.7 g/cm
3, then the density of sampling spot sample should control at 0.69 g/cm
3~ 0.71g/cm
3between;
E, High Temperature High Pressure oil well refers to oil well operation surface temperature at 150 ~ 240 ° of C, the oil well of the degree of depth below 4000 meters of oil well, ultimate compression strength is at 60 ~ 100MPa, the ultimate compression strength of well cementation test block depends on the ultimate compression strength of niobium (Nb) boride closed pore hollow ceramic microspheres, low pressure oil well refers to that ultimate compression strength is less than 20 MPa, temperature is at 70 ~ 90 ° of C, middle force feed well refers to that ultimate compression strength is at 20 ~ 60MPa, at 90 ~ 150 ° of C high pressure oil wells, temperature refers to that ultimate compression strength is greater than 60 ~ 100 MPa, temperature in oil well be surface temperature add oil well often decline 100 meters of temperature increase by 3 ° of C values and,
B, niobium (Nb) boride ceramic fine bead prepare oil well cementing test block:
The first step, batching: batching: be niobium (Nb) boride closed pore hollow ceramic microspheres 25 ~ 35 wt% of 5 ~ 50 μm, particle diameter 20 ~ 50 μm of flyash 5 ~ 7 wt% of loss on ignition 1.1%, purity 99.9% calcium oxide 1.5 ~ 2 wt%, sodium sulfate 0.5 ~ 1.0 wt% and micro-silicon 1 ~ 3 wt% of particle diameter 5 ~ 20 μm by G level oil well cement 55 ~ 65 wt%, particle diameter, the pH value of configuration slurries is between 8.0 ~ 10.5, G oil well cement particle diameter (at 180mesh) and niobium (Nb) boride closed pore hollow ceramic microspheres particle diameter (300 ~ 3000mesh) obvious difference, adopt the flyash of loss on ignition 1.1%, according to accumulation principle, space between the bi-material particle diameter that flyash mainly fills up G oil well cement and niobium (Nb) boride closed pore hollow ceramic microspheres, when the different particle of particle diameter is tangent between two, gap between tangent circles is filled by flyash, G oil well cement and glass microballon grain are combined closely, but usage quantity should control within the specific limits, namely control within the scope of 5 ~ 7 % of gross weight, otherwise, affect the intensity of high temperature high voltage resistant test block, next is through the flyash that high temperature sintering generates, there is activity, significantly improve the hydration rate of slurries, the flyash that loss on ignition is low needs water cement ratio little, the morning contributing to well cementation test block is strong, purity 99.9% calcium oxide, calcium oxide purity is higher, activity is stronger, hydration rate is fast, a large amount of heat is discharged during calcium oxide hydration reaction, and generate gelatinous material calcium hydroxide, the morning being beneficial to high temperature high voltage resistant slurries is strong, temperature plays an important role by force the morning to test block, secondly the calcium hydroxide generated after aquation is in alkalescence, the pH value of high temperature high voltage resistant slurries can be regulated, under weak basic condition, the early strength of high temperature high voltage resistant oil well cement can be improved, sodium sulfate is a kind of water retaining, it is obvious that dehydration effect falls, sodium ion in sodium sulfate, there is reverse osmosis function, velocity of diffusion is fast, make slurries in solidifying, separate out part water, sodium sulfate consumption is how many, the dehydration of falling of slurries is played an important role, rationally falling dehydration, to be conducive to morning of high temperature high voltage resistant Behavior of Hardened Cement Paste strong, if it is too much that dehydration falls in high temperature high voltage resistant slurries in solidifying, high temperature high voltage resistant well cementation test block shrinkage is large, cause blind hole, affect cementing quality, sodium sulfate is compared with other water retainings, sodium ion diffustivity is strong, diffusion uniformity, cost is low, Be very effective, according to accumulation principle, SILICA FUME mainly fills up G oil well cement and the gap between niobium (Nb) boride closed pore hollow ceramic microspheres and flyash, there is greater activity, form spawn, improve the intensity of high temperature high voltage resistant slurries, increasing dioxide-containing silica and slurries suspension stability and Behavior of Hardened Cement Paste high temperature resistance is indispensable technical qualification, above-mentioned several interpolation and must consumption be controlled,
Second step, make high temperature high voltage resistant well cementation test block: with 0.5 ~ 0.7(W/C) water cement ratio, adopt and slurries are aspirated by liquid pump, spray the outside surface of high speed rotating rotating cylinder, produce centrifugal force at outer surface of cylinder liquid slurry is shed, Stirring is shed in realization, and light-weight additive microballon is easily smashed by traditional blade high-speed stirring, slurries roll up and down and just can stir, pour part test into one group of two pieces of die trials, the length of die trial, wide, high 53mm*53mm*53mm respectively, maintenance 24 hours in the water-bath maintaining box of constant temperature 52 ° of C, 48 hours, soak 1 hour in cold water after the demoulding, carry out testing performance index, G level oil well cement 55 ~ 65 wt%, particle diameter is niobium (Nb) boride closed pore hollow ceramic microspheres 25 ~ 35 wt% of 20 ~ 50 μm, flyash 5 ~ 7 wt% of loss on ignition 1.1%, purity 99.9% calcium oxide 1.5 ~ 2 wt%, compound in sodium sulfate 0.5 ~ 1.0 wt% and micro-silicon 1 ~ 3 wt%, if water usage quantity is more than 0.5 ~ 0.7 scope, the grout cures time is long, early strength is low, it is too much that dehydration is fallen, test block is fallen dehydration and is greater than 50ml/30min, test block shrinkage is large, cause blind hole, affect cementing quality,
3rd step, testing performance index:
A, serum density measure: get second step and make slurries, pour in fluid densitometer and weigh density g/cm
3, the density of high temperature resistant, high pressure slurries is at 1.0 ~ 1.5g/cm
3between, test block rate of change of the density is less than 0.015 g/cm
3, according to ρ=m/V formula, weigh up the weight G of test block
1, according to volume V
1, bulk density ρ
1, test block is put on pressing machine and pressurizes, weigh up the weight G of test block
2, according to volume V
2,bulk density ρ
2, rate of change of the density is (ρ
2-ρ
1)/ρ
1, it is strong that rate of change of the density is less than explanation well cementation test block anti-pressure ability, V after pressurization
2volume change is little, density p
2change also little;
B, sedimentation stability: get second step making slurries and pour settlement barrel into, observe homogeneity after 0.5 hour, stability, homogeneity is that niobium (Nb) boride closed pore hollow ceramic microspheres and slurries merge mutually, no longer upper and lower floating fluctuation, and microballon is evenly distributed in slurries;
C, the performance test of raw-material performance and slurries: well cementing material can be divided into: base-material and G level oil well superfine cement, namely light-weight additive floats pearl and closed pore hollow ceramic microspheres, admixture, admixture refers to the material beyond base-material and light-weight additive, G level oil well superfine cement, niobium (Nb) boride hole hollow ceramic microspheres particle diameter, the loss on ignition of flyash and activity, the indexs such as the pH value of slurries, G level oil well superfine cement, niobium (Nb) boride hole hollow ceramic microspheres, the flyash of loss on ignition 1.1%, purity 99.9% calcium oxide, micro-silicon is all through the material of the high-temperature firing of 900 ° of more than C, the fusing point of salt sodium sulfate 884 ° of C, not easily decompose in High Temperature High Pressure oil well, stability is strong, adopt the flyash of loss on ignition 1.1%, loss on ignition is low, carbon content is low, sintering fully, active high, hydration reaction speed is fast, form gelatinous material speed fast, according to accumulation principle, space between the bi-material particle diameter that flyash mainly fills up G oil well cement and closed pore hollow glass micropearl, when the different particle of particle diameter is tangent between two, gap between tangent circles is filled by flyash, G oil well cement and the hollow glass microballon grain of niobium (Nb) boride closed pore are combined closely, but usage quantity should control within the specific limits, namely control within the scope of 5 ~ 7 % of gross weight, otherwise, affect the intensity of test block, next is through the flyash that high temperature sintering generates, there is activity, the hydration rate of slurries is accelerated, the morning contributing to well cementation test block is strong, purity 99.9% calcium oxide, calcium oxide purity is higher, activity is stronger, hydration rate is fast, a large amount of heat is discharged during calcium oxide hydration reaction, the temperature of slurries is raised, and generate gelatinous material calcium hydroxide, the morning being beneficial to test block is strong, secondly the calcium hydroxide generated after aquation is in alkalescence, the pH value of slurries can be regulated, under weak basic condition, namely pH value is between 8 ~ 10.5, the early strength of oil well test block can be improved, sodium sulfate is a kind of water retaining, it is obvious that dehydration effect falls, sodium ion in sodium sulfate, there is reverse osmosis function, velocity of diffusion is fast, make slurries in solidifying, separate out part water, sodium sulfate consumption is how many, the dehydration of falling of slurries is played an important role, rationally falling dehydration, to be conducive to morning of Behavior of Hardened Cement Paste strong, if it is too much that dehydration falls in slurries in solidifying, well cementation test block shrinkage is large, cause blind hole, affect cementing quality, sodium sulfate is compared with other water retainings, sodium ion diffustivity is strong, diffusion uniformity, cost is low, Be very effective, admixture must control usage quantity, flyash consumption is excessive, the ultimate compression strength of well cementation test block reduces, density increases, water cement ratio increases, namely water consumption increases, fall dehydration to increase, light-weight additive can not be replaced with admixture, more can not replace basic oil well cement with admixture, the intensity of loss test block, the density of slurries can be increased, ultimate compression strength reduces, test block of even cementing the well does not have ultimate compression strength and folding strength, light-weight additive and admixture must control consumption, use range and condition need be shown especially, although some admixture has similar function to the admixture of above-mentioned use, but the environment used is different, environment for use changes admixture will lose function, conventional admixture is as hardening accelerator, water retaining, setting accelerator is low temperature modification, use at 90 ° of below C, otherwise lost efficacy, other admixture is as flyash, calcium oxide, micro-silicon etc. must limit purity, composition, color, addition, the indexs such as the scope used, carry out parametrization demarcation, what both wanted arrives, that also must do in technical publications arrives, namely for high temperature high voltage resistant well cementation test block, well cementation is greater than 4000 meters, use temperature is at 150 ~ 240 ° of C, test block pressure resistance intensity is at 60 ~ 100MPa, namely the niobium (Nb) boride bead density of high temperature high voltage resistant well cementation test block is prepared at 0.5g/cm
3~ 0.85 g/cm
3between, and flyash, silica flour, wilkinite, kaolin, diatomite, sepiolite antisaline soil isodensity are all at 2.0 g/cm
3above, density can not be prepared at 1.0 ~ 1.5g/cm
3between slurries, usually by 1.0 ~ 1.5g/cm
3between be high temperature high voltage resistant slurries, 1.6 g/cm
3~ 1.7 g/cm
3for the slurries of resistance to medium temperature and medium pressure, 1.8 g/cm
3~ 1.9 g/cm
3for low-temperature low pressure resistance slurries, and G level oil well superfine cement density is at 3.0 ~ 3.3g/cm
3, density adopts weighted average calculation,
D, thickening time: vary with temperature obviously, also adds quantity kind with admixture relevant, records the thickening time;
E, because High Temperature High Pressure oil well operation surface temperature is at 150 ~ 240 ° of C, conventional admixture is if the scope of applications such as hardening accelerator, dispersion agent, water retaining, setting accelerator, defoamer are at 90 ° of below C, temperature raises admixture and decomposes ineffective, the temperature use range of admixture must be shown, otherwise admixture lost efficacy;
F, high temperature resistant, high pressure be well cementation test block in 150 ~ 240 ° of C temperature ranges, ultimate compression strength is between 60 ~ 100MPa, and test block rate of change of the density is less than 0.015 g/cm
3, between necessary consistent with cement size 5 ~ 50 μm of the particle diameter of the light-weight additive used, because light-weight additive density is less than the density of water, at 0.5 ~ 0.85 g/cm
3, particle diameter is larger, expanding volume is large, wall is thinner, ultimate compression strength declines, the filling doses such as the flyash needed are large, density becomes large, water cement ratio increases, Large stone macrobead floats in High Temperature High Pressure slurries, the large sinking of cement density, make the layering of High Temperature High Pressure slurries, cause well cementation layer Density inhomogeneity, there is blind hole, to collaborate phenomenon, light-weight additive (referring to the light-weight additives such as the drift pearl in flyash) ultimate compression strength is low, be less than 20MPa, after pressurization, percentage of damage is high, density increases, cause oil well blind hole, light-weight additive performance is the key factor of High Temperature High Pressure oil well well cementation success or failure.
Described niobium (Nb) boride ceramic fine bead prepares the method for high temperature high voltage resistant oil well cementing test block, and the high temperature high voltage resistant oil well cementing test block of preparation is fallen fluid loss and is less than 50ml/30min.
Described niobium (Nb) boride ceramic fine bead prepares the method for high temperature high voltage resistant oil well test block, and test block rate of change of the density is less than 0.015 g/cm
3, according to ρ=m/V formula, weigh up the weight G of test block
1, according to volume V
1, bulk density ρ
1, test block is put on pressing machine and pressurizes, weigh up the weight G of test block
2, according to volume V
2,bulk density ρ
2, rate of change of the density is (ρ
2-ρ
1)/ρ
1, it is strong that rate of change of the density is less than explanation test block anti-pressure ability, V after pressurization
2volume change is little, in the constant situation of weight, and density p
2change also little.
The present invention has the following advantages.
1, can change the dependence to flyash floating bead in long-term well cementation, the density of ceramic fine bead, wall thickness, sintering temperature can control.
2, this technical matters is advanced, and technology maturation, product performance are stable, and production cost is low, and output is high, and performance is good, opens well cementation synthesis virgin material new way.
3
,niobium (Nb) boride ceramic fine bead density is at 0.50 g/cm
3~ 0.85g/cm
3, according to piling up the theoretical space added between SILICA FUME filler particles, dioxide-containing silica is high, increase Behavior of Hardened Cement Paste high temperature resistance, G level oil well cement, ceramic fine bead have greater activity through 1000 ° of more than C high temperature sinterings, and hydration reaction is fast, can jelly be formed, can early strength be improved.
4
,through overexpansion on the oxygenation gas furnace of zonal control, high temperature sintering, melt surface vitreous, balling-up, the concentration of oxygen is 30 ~ 35%, the concentration of oxygen is higher, burning-point is lower, burn more abundant, the heat of release is more, temperature is higher, adopt high pressure spraying high speed centrifugation rotary spraying technique, body of heater is entered after slurries body is fully atomized, drop is at breathing space expanded by heating, expanding volume is relevant with expansion temperature and density of foaming agent, again through sintering, melting, last balling-up, prevent knot wall from adopting thermal cycling air-bleed system to improve output, blower fan adopts speed control by frequency variation blower fan.
Embodiment
Embodiment 1.
Niobium (Nb) boride ceramic fine bead prepares the method for high temperature high voltage resistant oil well cementing test block, comprise the preparation of niobium (Nb) boride closed pore hollow ceramic microspheres, batching, mixing, stirring sized mixing, die trial, performance test, niobium (Nb) boride closed pore hollow ceramic close microballon performance test comprise its floatability mensuration, density, resistance to hydrostatic pressure intensity mensuration, serum density mensuration, sedimentation stability, thickening time, fall fluid loss, withstand voltage density test, the liquidity scale, carry out compressive property test.
Comprise the following steps:
Prepared by A, niobium (Nb) boride closed pore hollow ceramic microspheres:
B, the first step are prepared burden: by particle diameter 1 ~ 5 μm of Niobium Pentxoxide powder, 3 ~ 10 μm of boron carbide powders and 5 ~ 10 μm of boron oxides be in proportion: 7 5wt%:20 wt%:5 wt%.
Second step, base: by particle diameter 1 ~ 5 μm of Niobium Pentxoxide powder, 3 ~ 10 μm of boron carbide powders and 5 ~ 10 μm of boron oxides are in proportion: 7 5wt%:20 wt%:5 wt% samplings are mixed to get powder mix, by particle diameter 1 ~ 5 μm of Niobium Pentxoxide powder, resol is added in 3 ~ 10 μm of boron carbide powders and 5 ~ 10 μm of boron oxide powder mixs, part by weight is: 1 wt%:0.5 wt%, by particle diameter 1 ~ 5 μm of Niobium Pentxoxide powder, 3 ~ 10 μm of boron carbide powders and 5 ~ 10 μm of boron oxide powder mixs and resol mixing and stirring, solidification treatment at 50 ° of C temperature, cured body is pulverized in powder-making machine, obtain 30 μm of powder mixs, compound puts into mould, pressing machine applies 2MPa pressure, extrusion molding obtains blank.
3rd step, high-temperature firing: second step is obtained blank and puts into high temperature sintering furnace, under 1600 ° of C, be 6 hours in the time of hydrogen atmosphere heat preservation sintering, 300 ° of C carbonization treatment obtain niobium boride powder.
The making of the 4th step, niobium (Nb) boride solid microbeads: the 3rd step obtains niobium boride powder and be processed into 20 μm of niobium (Nb) boride solid microbeads on balling machine.
5th step, niobium (Nb) boride liquid slurry makes: the per-cent of niobium (Nb) boride liquid slurry consists of: 20 μm of niobium (Nb) boride 65 wt%: water 35 wt%.
6th step, whipping agent add: in the niobium (Nb) boride liquid slurry that the 5th step makes, add whipping agent, the one in calcium carbonate, potassium sulfate or sodium sulfate, concentration is 1g/L.
Prepared by the 7th step, niobium (Nb) boride closed pore hollow ceramic microspheres: the 6th step mixed solution is starched abundant agitation and filtration, adopt high pressure spraying high speed centrifugation rotary spraying technique, form microballoon, expansion temperature that the oxygenation gas furnace of zonal control dewaters 800 ° of C, oven dry sintering temperature are at 1400 ° of C, melt surface temperature 1700 ° of C, one-tenth bulb temperature 1400 ° of C, and balling-up selects classification to obtain 10 μm of niobium (Nb) boride closed pore hollow ceramic microspheres through wind power Cheongju.
8th step, testing performance index: a, its floatability measure: get 10 μm of niobium (Nb) boride closed pore hollow ceramic microspheres 100 grams, first will pour in the beaker of 1000 milliliters, pour 500 ml tap waters again in beaker, stir with glass stick, leave standstill 1 hour, niobium (Nb) boride closed pore hollow ceramic microspheres floating in beaker is drift pearl, heavy pearl is precipitated as in beaker bottom, take out respectively and dry weigh floating pearl and heavy pearl in beaker, calculate its floatability, its floatability of niobium (Nb) boride closed pore hollow ceramic microspheres in water is greater than 98%.
B, measure the density of niobium (Nb) boride closed pore hollow ceramic microspheres: the volumetric flask getting 100 milliliters is weighed G
1, then niobium (Nb) boride closed pore hollow ceramic microspheres is poured in 100 milliliters of volumetric flasks, the scale marks of niobium (Nb) boride closed pore hollow ceramic microspheres concave surface and 100 milliliters of volumetric flasks is tangent, and weighing niobium (Nb) boride closed pore hollow ceramic microspheres and bottle are heavily G
2, 100 milliliters of niobium (Nb) boride closed pore hollow ceramic microspheres nt wt net weights are G
2-G
1, according to m=ρ V, density=(G
2-G
1)/V, niobium (Nb) boride closed pore hollow ceramic microspheres is at 0.5g/cm
3.
The mensuration of c, resistance to hydrostatic pressure intensity: weigh niobium (Nb) boride closed pore hollow ceramic microspheres 100 grams and pour in hydrostaticpressure intensity test tube, hydrostaticpressure intensity test tube is connected with pressure pump, water in pressure pump is stressed in hydrostaticpressure intensity test tube, record force value, the niobium (Nb) boride closed pore hollow ceramic microspheres stopping pressurization taking out in test tube measures its floatability, intensity 150 MPa of niobium (Nb) boride closed pore hollow ceramic microspheres resistance to hydrostatic pressure.
B, niobium (Nb) boride ceramic fine bead prepare the test block of high temperature high voltage resistant oil well cementing:
The first step, batching: be niobium (Nb) boride closed pore hollow ceramic microspheres 35 wt% of 10 μm, flyash 5 wt% of loss on ignition 1.1%, purity 99.9% calcium oxide 1.5 wt%, sodium sulfate 0.5 wt% and micro-silicon 3 wt% by G level oil well cement 55wt%, particle diameter.
Second step, make high temperature high voltage resistant well cementation test block: with 0.5(W/C) water cement ratio stir in stirrer and size mixing 40 seconds, pour one group of two pieces of die trial into, the length 53mm*53mm*53mm respectively of die trial, maintenance 24 hours, 48 hours in the water-bath maintaining box of constant temperature 52 ° of C, soak 1 hour in cold water after the demoulding, carry out testing performance index.
3rd step, testing performance index: a, serum density measure: get second step and make high temperature high voltage resistant slurries, pour in mud scale and weigh density g/cm
3, the density of high temperature high voltage resistant slurries is at 1.1g/cm
3between.
B, sedimentation stability: get second step making high temperature high voltage resistant slurries and pour settlement barrel into, observe homogeneity after 0.5 hour, stability, homogeneity is that niobium (Nb) boride closed pore hollow ceramic microspheres and slurries merge mutually, no longer upper and lower floating fluctuation, microballon is evenly distributed in slurries.
C, thickening time: vary with temperature.
The mensuration of well cementation test block rate of change of the density, measure 24 and 48 hours well cementation test block density, well cementation test block is put into pressing machine pressurization (80 MPa, 120 MPa, 150 MPa, 200 MPa) measure the well cementation test block density after pressurizeing, rate of change of the density equals: (after pressurization, density deducts 24 and 48 hours well cementation test block density)/24 and 48 hours well cementation test block density, if rate of change of the density is greater than 0.02, illustrate that nitrogenize niobium (Nb) boride closed pore hollow ceramic microspheres inhomogeneity of wall thickness is even, percentage of damage is high, after pressurization, density increases, do not reach standard, the degree of rate of change of the density and off-design density, the density of well cementation test block equals the well cementation quality of test block and the ratio of volume.
(12) maintenance 24 hours in the water-bath maintaining box of constant temperature 52 ° of C, soaks 1 hour after the demoulding in cold water, carries out ultimate compression strength and folding strength test by being defined on pressing machine of GB GB/T 177.
13) maintenance 48 hours in the water-bath maintaining box of constant temperature 52 ° of C, soaks 1 hour after the demoulding in cold water, carries out ultimate compression strength and folding strength test by being defined on pressing machine of GB GB/T 177.
Embodiment 2.
Niobium (Nb) boride ceramic fine bead prepares the method for high temperature high voltage resistant oil well cementing test block, comprise the preparation of niobium (Nb) boride closed pore hollow ceramic microspheres, batching, mixing, stirring sized mixing, die trial, performance test, niobium (Nb) boride Ceramic Composite closed pore cenosphere performance test comprise its floatability mensuration, density, resistance to hydrostatic pressure intensity mensuration, serum density mensuration, sedimentation stability, thickening time, fall fluid loss, withstand voltage density test, the liquidity scale, carry out compressive property test.
Comprise the following steps:
Prepared by A, niobium (Nb) boride closed pore hollow ceramic microspheres:
The first step, batching: by particle diameter 6 ~ 10 μm of Niobium Pentxoxide powder, 15 ~ 20 μm of boron carbide powders and, 10 ~ 15 μm of boron oxides,
Be by weight percentage: 80wt%:14 wt%:6 wt%.
Second step, base: by particle diameter 6 ~ 10 μm of Niobium Pentxoxide powder, 15 ~ 20 μm of boron carbide powders and, 10 ~ 15 μm of boron oxides are in proportion: 80wt%:14 wt%:6 wt% sampling is mixed to get powder mix, by particle diameter 6 ~ 10 μm of Niobium Pentxoxide powder, 15 ~ 20 μm of boron carbide powders and, resol is added in 10 ~ 15 μm of boron oxide powder mixs, part by weight is: 1 wt%:0.8 wt%, by particle diameter 6 ~ 10 μm of Niobium Pentxoxide powder, 15 ~ 20 μm of boron carbide powders and, 10 ~ 15 μm of boron oxide powder mixs and resol mixing and stirring, solidification treatment at 80 ° of C temperature, cured body is pulverized in powder-making machine, obtain 50 μm of powder mixs, compound puts into mould, pressing machine applies 2.5MPa pressure, extrusion molding obtains blank.
3rd step, high-temperature firing: second step is obtained blank and puts into high temperature sintering furnace, under 1800 ° of C, be 8 hours in the time of hydrogen atmosphere heat preservation sintering, 500 ° of C carbonization treatment obtain niobium boride powder.
The making of the 4th step, niobium (Nb) boride solid microbeads: the 3rd step obtains niobium boride powder and be processed into 30 μm of niobium (Nb) boride solid microbeads on balling machine.
5th step, niobium (Nb) boride liquid slurry makes: the per-cent of niobium (Nb) boride liquid slurry consists of: 30 μm of niobium (Nb) boride 70 wt%: water 30 wt%.
6th step, whipping agent add: in the niobium (Nb) boride liquid slurry that the 5th step makes, add whipping agent, the one in calcium carbonate, potassium sulfate or sodium sulfate, concentration is 1.5g/L.
Prepared by the 7th step, niobium (Nb) boride closed pore hollow ceramic microspheres: the 6th step mixed solution is starched abundant agitation and filtration, adopt high pressure spraying high speed centrifugation rotary spraying technique, form microballoon, expansion temperature that the oxygenation gas furnace of zonal control dewaters 820 ° of C, oven dry sintering temperature are at 1500 ° of C, melt surface temperature 1800 ° of C, one-tenth bulb temperature 1450 ° of C, and balling-up selects classification to obtain 20 μm of niobium (Nb) boride closed pore hollow ceramic microspheres through wind power Cheongju.
8th step, testing performance index: a, its floatability measure: get 20 μm of niobium (Nb) boride closed pore hollow ceramic microspheres 100 grams, first will pour in the beaker of 1000 milliliters, pour 500 ml tap waters again in beaker, stir with glass stick, leave standstill 1 hour, niobium (Nb) boride closed pore hollow ceramic microspheres floating in beaker is drift pearl, heavy pearl is precipitated as in beaker bottom, take out respectively and dry weigh floating pearl and heavy pearl in beaker, calculate its floatability, its floatability of niobium (Nb) boride closed pore hollow ceramic microspheres in water is greater than 98%.
B, measure the density of niobium (Nb) boride closed pore hollow ceramic microspheres: the volumetric flask getting 100 milliliters is weighed G
1, then niobium (Nb) boride closed pore hollow ceramic microspheres is poured in 100 milliliters of volumetric flasks, the scale marks of niobium (Nb) boride closed pore hollow ceramic microspheres concave surface and 100 milliliters of volumetric flasks is tangent, and weighing niobium (Nb) boride closed pore hollow ceramic microspheres and bottle are heavily G
2, 100 milliliters of niobium (Nb) boride closed pore hollow ceramic microspheres nt wt net weights are G
2-G
1, according to m=ρ V, density=(G
2-G
1)/V, niobium (Nb) boride closed pore hollow ceramic microspheres is at 0.5g/cm
3.
The mensuration of c, resistance to hydrostatic pressure intensity: weigh niobium (Nb) boride closed pore hollow ceramic microspheres 100 grams and pour in hydrostaticpressure intensity test tube, hydrostaticpressure intensity test tube is connected with pressure pump, water in pressure pump is stressed in hydrostaticpressure intensity test tube, record force value, the niobium (Nb) boride closed pore hollow ceramic microspheres stopping pressurization taking out in test tube measures its floatability, intensity 120 MPa of niobium (Nb) boride closed pore hollow ceramic microspheres resistance to hydrostatic pressure.
B, niobium (Nb) boride ceramic fine bead prepare the test block of high temperature high voltage resistant oil well cementing:
The first step, batching: be niobium (Nb) boride closed pore hollow ceramic microspheres 30 wt% of 20 μm, flyash 5.5 wt% of loss on ignition 1.1%, purity 99.9% calcium oxide 1.5 wt%, sodium sulfate 0.5 wt% and micro-silicon 2.5 wt% by G level oil well cement 60wt%, particle diameter.
Second step, make high temperature high voltage resistant well cementation test block: with 0.6(W/C) water cement ratio stir in stirrer and size mixing 40 seconds, pour one group of two pieces of die trial into, the length 53mm*53mm*53mm respectively of die trial, maintenance 24 hours, 48 hours in the water-bath maintaining box of constant temperature 52 ° of C, soak 1 hour in cold water after the demoulding, carry out testing performance index.
3rd step, testing performance index: a, serum density measure: get second step and make high temperature high voltage resistant slurries, pour in mud scale and weigh density g/cm
3, the density of high temperature high voltage resistant slurries is at 1.25g/cm
3between.
B, sedimentation stability: get second step making high temperature high voltage resistant slurries and pour settlement barrel into, observe homogeneity after 0.5 hour, stability, homogeneity is that niobium (Nb) boride closed pore hollow ceramic microspheres and slurries merge mutually, no longer upper and lower floating fluctuation, microballon is evenly distributed in slurries.
C, thickening time: vary with temperature, record data.
The mensuration of well cementation test block rate of change of the density, measure 24 and 48 hours well cementation test block density, well cementation test block is put into pressing machine pressurization (60MPa, 75MPa, 100 MPa, 150 MPa, 200 MPa, 250 MPa) measure the well cementation test block density after pressurizeing, rate of change of the density equals: (after pressurization, density deducts 24 and 48 hours well cementation test block density)/24 and 48 hours well cementation test block density, if rate of change of the density is greater than 0.02, illustrate that nitrogenize niobium (Nb) boride closed pore hollow ceramic microspheres inhomogeneity of wall thickness is even, percentage of damage is high, after pressurization, density increases, do not reach standard, the degree of rate of change of the density and off-design density, the density of well cementation test block equals the well cementation quality of test block and the ratio of volume.
Maintenance 24 hours in the water-bath maintaining box of constant temperature 52 ° of C, soaks 1 hour after the demoulding in cold water, carries out ultimate compression strength and folding strength test by being defined on pressing machine of GB GB/T 177.
Note: G level oil well cement is Qi Yin cement mill, Shandong, the prosperous sub-calcium industry of purity 99.9% calcium oxide Shandong Zibo, the flyash Huaneng Group Xin Dian power plant of loss on ignition 1.1%.
Claims (2)
1. niobium (Nb) boride ceramic fine bead prepares the method for high temperature high voltage resistant oil well cementing test block, comprise the preparation of niobium (Nb) boride closed pore hollow ceramic microspheres, batching, mixing, stirring sized mixing, die trial, performance test, niobium (Nb) boride closed pore hollow ceramic microspheres performance test comprise its floatability mensuration, density, resistance to hydrostatic pressure intensity mensuration, serum density mensuration, sedimentation stability, thickening time, fall fluid loss, withstand voltage density test, the liquidity scale, carry out compressive property test;
Comprise the following steps:
Prepared by A, niobium (Nb) boride closed pore hollow ceramic microspheres:
The first step, batching: get particle diameter 1 ~ 10 μm of Niobium Pentxoxide powder, particle diameter 3 ~ 20 μm of boron carbide powders and, particle diameter 5 ~ 15 μm of boron oxide ratios are: wt%:3 ~ 6,70 ~ 80wt%:15 ~ 20 wt%;
Second step, base: by particle diameter 1 ~ 10 μm of Niobium Pentxoxide powder, particle diameter 3 ~ 20 μm of boron carbide powders and, particle diameter 5 ~ 15 μm of boron oxides are mixed to get powder mix by the weight percent sampling of the first step, by particle diameter 1 ~ 10 μm of Niobium Pentxoxide powder, particle diameter 3 ~ 20 μm of boron carbide powders and, resol is added in particle diameter 5 ~ 15 μm of boron oxide powder mixs, part by weight is: 1.0 wt%:0.5 ~ 0.8 wt%, by particle diameter 1 ~ 10 μm of Niobium Pentxoxide powder, particle diameter 3 ~ 20 μm of boron carbide powders and, with resol mixing and stirring in particle diameter 5 ~ 15 μm of boron oxide powder mixs, solidification treatment at 50 ~ 100 ° of C temperature, cured body is pulverized in powder-making machine, obtain particle diameter 30 ~ 100 μm of powder mixs, compound puts into mould, pressing machine applies 1 ~ 3 MPa pressure, extrusion molding obtains blank,
3rd step, high-temperature firing: second step is obtained blank and puts into high temperature sintering furnace, under 1600 ~ 2000 ° of C, be 5 ~ 8 hours in the time of hydrogen atmosphere stove heat preservation sintering, 300 ~ 500 ° of C carbonization treatment obtain niobium boride powder;
The making of the 4th step, niobium (Nb) boride solid microbeads: the 3rd step is obtained niobium boride powder and be processed into particle diameter 5 ~ 30 μm of niobium (Nb) boride solid microbeads powder on balling machine;
5th step, niobium (Nb) boride liquid slurry makes: the per-cent of niobium (Nb) boride liquid slurry consists of: particle diameter 5 ~ 30 μm of niobium (Nb) boride 60 ~ 70 wt%: water 30 ~ 40 wt%;
6th step, whipping agent add: in the niobium (Nb) boride liquid slurry that the 5th step makes, add whipping agent, the one in calcium carbonate, potassium sulfate or sodium sulfate, concentration is 1 ~ 3g/L;
Prepared by the 7th step, niobium (Nb) boride closed pore hollow ceramic microspheres: the 6th step mixed solution is starched abundant agitation and filtration, adopt high pressure spraying high speed centrifugation rotary spraying technique, form microballoon, through overexpansion, high temperature sintering, melt surface vitreous, balling-up on the oxygenation gas furnace of zonal control, select classification to obtain 5 ~ 50 μm of niobium (Nb) boride closed pore hollow ceramic microspheres, niobium (Nb) boride closed pore hollow ceramic microspheres wall thickness at 10 ~ 20 μm through Feng Li Cheongju, ultimate compression strength is at 110 ~ 250 MPa;
8th step, testing performance index:
A, its floatability measure: take particle diameter 5 ~ 50 μm of niobium (Nb) boride closed pore hollow ceramic microspheres 100 grams, pour in the beaker of 1000 milliliters, pour 500 ml tap waters again into fall in beaker, stir with glass stick, leave standstill 1 hour, niobium (Nb) boride closed pore hollow ceramic microspheres floating in beaker is drift pearl, heavy pearl is precipitated as in beaker bottom, take out respectively and dry weigh floating pearl and heavy pearl in beaker, calculate its floatability, its floatability of niobium (Nb) boride closed pore hollow ceramic microspheres in water is greater than 98%;
B, measure the density of niobium (Nb) boride closed pore hollow ceramic microspheres: the volumetric flask getting 100 milliliters is weighed to obtain G
1, then niobium (Nb) boride closed pore hollow ceramic microspheres is poured in 100 milliliters of volumetric flasks, the scale marks of niobium (Nb) boride closed pore hollow ceramic microspheres concave surface and 100 milliliters of volumetric flasks is tangent, weighs niobium (Nb) boride closed pore hollow ceramic microspheres and bottle recuperation G
2, 100 milliliters of niobium (Nb) boride closed pore hollow ceramic microspheres nt wt net weights are G
2-G
1, obtain m=ρ V according to quality, density and volume, density p=(G
2-G
1)/V, according to the cementing requirements of High Temperature High Pressure well cementation test block, test block density is at 1.0 ~ 1.5g/cm
3, and niobium (Nb) boride closed pore hollow ceramic microspheres density is at 0.5g/cm
3~ 0.85 g/cm
3between;
The mensuration of c, resistance to hydrostatic pressure intensity: weigh niobium (Nb) boride closed pore hollow ceramic microspheres 100 grams and pour in hydrostaticpressure intensity test tube, hydrostaticpressure intensity test tube is connected with pressure pump, water in pressure pump is stressed in hydrostaticpressure intensity test tube, record force value, the niobium (Nb) boride closed pore hollow ceramic microspheres stopping pressurization taking out in test tube measures its floatability, and the intensity of niobium (Nb) boride closed pore hollow ceramic microspheres resistance to hydrostatic pressure is at 110 ~ 250MPa;
The variable density value of d, detection niobium (Nb) boride closed pore hollow ceramic microspheres: the variable density scope of the niobium (Nb) boride closed pore hollow ceramic microspheres of the sampling spot of same batch of different positions is at ± 0.01 g/cm
3;
E, high temperature high voltage resistant oil well refers to oil well operation surface temperature at 150 ~ 240 ° of C, the oil well of the degree of depth below 4000 meters of oil well, ultimate compression strength is at 60 ~ 100MPa, the ultimate compression strength of well cementation test block depends on the ultimate compression strength of niobium (Nb) boride closed pore hollow ceramic microspheres, low-pressure low-temperature oil well refers to that the degree of depth is less than 2000 meters, ultimate compression strength is less than 20 MPa, temperature is at 70 ~ 90 ° of C, in middle pressure, warm oil well refers to that the degree of depth is at 2000 ~ 4000 meters, ultimate compression strength is at 20 ~ 60MPa, at 90 ~ 150 ° of C high pressure-temperature oil wells, temperature refers to that the degree of depth is greater than 4000 meters, ultimate compression strength is greater than 60 ~ 100MPa,
b, niobium (Nb) boride ceramic fine bead prepare the test block of high temperature high voltage resistant oil well cementing:
The first step, batching: batching: be niobium (Nb) boride closed pore hollow ceramic microspheres 25 ~ 35 wt% of 5 ~ 50 μm, particle diameter 20 ~ 50 μm of flyash 5 ~ 7 wt% of loss on ignition 1.1%, purity 99.9% calcium oxide 1.5 ~ 2 wt%, sodium sulfate 0.5 ~ 1.0 wt% and micro-silicon 1 ~ 3 wt% of particle diameter 5 ~ 20 μm by G level oil well cement 55 ~ 65 wt%, particle diameter, the pH value of configuration slurries is between 8.0 ~ 10.5;
Second step, make High Temperature High Pressure well cementation test block: with 0.5 ~ 0.7(W/C) water cement ratio, slurries are aspirated by liquid pump, spread the outside surface of high speed rotating rotating cylinder, produce centrifugal force at outer surface of cylinder to be shed by liquid slurry, realize rotary spreading and stir, one group of two pieces of die trial is poured in part test into, the length 53mm*53mm*53mm respectively of die trial, maintenance 24 hours, 48 hours in the water-bath maintaining box of constant temperature 52 ° of C, soaks 1 hour after the demoulding, carries out testing performance index in cold water;
3rd step, testing performance index:
The density measurement of a, slurries: get second step and make High Temperature High Pressure slurries, pour in mud scale and weigh density and reading, the density of high temperature high voltage resistant slurries is at 1.0 ~ 1.5g/cm
3between;
B, sedimentation stability: get second step making High Temperature High Pressure slurries and pour settlement barrel into, observe homogeneity after 0.5 hour, stability, homogeneity is that niobium (Nb) boride closed pore hollow ceramic microspheres and slurries merge mutually, no longer upper and lower floating fluctuation, microballon is evenly distributed in the slurries of settlement barrel;
C, the performance test of raw-material performance and slurries: well cementing material can be divided into: base-material and G level oil well superfine cement, namely light-weight additive floats pearl or closed pore hollow ceramic microspheres, admixture, admixture refers to the material beyond base-material and light-weight additive, measure G level oil well superfine cement, niobium (Nb) boride closed pore hollow ceramic microspheres particle diameter, the loss on ignition of flyash and activity, the indexs such as the pH value of slurries, G level oil well superfine cement, niobium (Nb) boride closed pore hollow ceramic microspheres, the flyash of loss on ignition 1.1%, purity 99.9% calcium oxide, micro-silicon is all through the material of the high-temperature firing of 900 ° of more than C, what high-temperature electric resistance furnace temperature referred to is greater than 900 ° of C, the fusing point of salt sodium sulfate 884 ° of C, not easily decompose in High Temperature High Pressure oil well, stability is strong, adopt the flyash of loss on ignition 1.1%, loss on ignition is low, carbon content is low, sintering fully, active high, hydration reaction speed is fast, form gelatinous material speed fast, according to accumulation principle, space between the bi-material particle diameter that flyash mainly fills up G oil well superfine cement and closed pore hollow glass micropearl, when the different particle of particle diameter is tangent between two, gap between tangent circles is filled by flyash, G oil well cement and the hollow glass microballon grain of closed pore are combined closely, but usage quantity should control within the specific limits, namely control within the scope of 5 ~ 7 % of gross weight, otherwise, affect the intensity of test block, increase water cement ratio, fall dehydration to increase, shrink large blind hole, next is through the flyash that high temperature sintering generates, there is activity, the hydration rate of slurries is accelerated, the flyash that loss on ignition is low needs water cement ratio little, the morning contributing to well cementation test block is strong, purity 99.9% calcium oxide, calcium oxide purity is higher, activity is stronger, hydration rate is fast, a large amount of heat is discharged during calcium oxide hydration reaction, the temperature of slurries is raised, and generate gelatinous material calcium hydroxide, the morning being beneficial to high temperature high voltage resistant test block is strong, temperature plays an important role by force the morning to test block, secondly the calcium hydroxide generated after aquation is in alkalescence, the pH value of slurries can be regulated, under weak basic condition, namely pH value is between 8 ~ 10.5, the early strength of oil well cement can be improved, sodium sulfate is a kind of water retaining, it is obvious that dehydration effect falls, sodium ion in sodium sulfate, there is reverse osmosis function, velocity of diffusion is fast, make slurries in solidifying, separate out part water, sodium sulfate consumption is how many, the dehydration of falling of slurries is played an important role, rationally falling dehydration, to be conducive to morning of Behavior of Hardened Cement Paste strong, if it is too much that dehydration falls in slurries in solidifying, well cementation test block shrinkage is large, cause blind hole, affect cementing quality, sodium sulfate is compared with other water retainings, sodium ion diffustivity is strong, diffusion uniformity, cost is low, Be very effective, in silica flour, dioxide-containing silica is high, improve the ultimate compression strength of well cementation test block, admixture must control usage quantity, light-weight additive can not be replaced with admixture, more can not replace basic oil well cement with admixture, the intensity of loss test block, the density of niobium (Nb) boride ceramic fine bead should at 0.5g/cm
3~ 0.85 g/cm
3between, and flyash, silica flour, wilkinite, kaolin, diatomite, sepiolite antisaline soil isodensity are all at 2.0 g/cm
3above, density can not be prepared at 1.0 ~ 1.5g/cm
3between slurries, usually by 1.0 ~ 1.5g/cm
3between slurries be high temperature high voltage resistant slurries, 1.6 g/cm
3~ 1.7 g/cm
3for the slurries of resistance to medium temperature and medium pressure, 1.8 g/cm
3~ 1.9 g/cm
3for low-temperature low pressure resistance slurries, density is different, and the well cementation scope be suitable for is different, and G level oil well superfine cement density is at 3.0 ~ 3.3g/cm
3, density calculation adopts weighted mean,
d, thickening time: vary with temperature obviously, also adds quantity kind with admixture relevant, records the thickening time;
E, because High Temperature High Pressure oil well operation surface temperature is at 150 ~ 240 ° of C, conventional admixture is if the scope of applications such as hardening accelerator, dispersion agent, water retaining, setting accelerator, defoamer are at 90 ° of below C, temperature raises admixture and decomposes ineffective, and the admixture that high temperature high voltage resistant oil well uses need indicate the working conditionss such as temperature resistant range especially;
F, high temperature resistant, high pressure be well cementation test block in 150 ~ 240 ° of C temperature ranges, ultimate compression strength is between 60 ~ 100MPa, and test block rate of change of the density is less than 0.015 g/cm
3;
G
,the restriction of light-weight additive and admixture content: the add-on that light-weight additive refers to niobium (Nb) boride closed pore hollow ceramic microspheres should be less than or equal to 35 wt %, admixture heatproof must be greater than 300 ° of C, addition controls within the specific limits, i.e. flyash 5 ~ 7 wt% of loss on ignition 1.1%, purity 99.9% calcium oxide 1.5 ~ 2 wt%, sodium sulfate 0.5 ~ 1.0 wt% and micro-silicon 1 ~ 3 wt%.
2. niobium (Nb) boride ceramic fine bead according to claim 1 prepares the method for high temperature high voltage resistant oil well cementing test block, it is characterized in that: the High Temperature High Pressure well cementation test block of preparation is fallen fluid loss and is less than 50ml/30min.
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| CN102285662A (en) * | 2011-05-25 | 2011-12-21 | 山东理工大学 | Preparation method of niobium boride powder |
| CN103833286A (en) * | 2014-03-11 | 2014-06-04 | 山东理工大学 | Method for preparing low-density oil well cement test block by using zirconium diboride ceramic micro-beads |
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| CN103833286A (en) * | 2014-03-11 | 2014-06-04 | 山东理工大学 | Method for preparing low-density oil well cement test block by using zirconium diboride ceramic micro-beads |
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