Amorphous nickel-tungsten-phosphorus alloy electroplating solution applied to electroplating of oil-well pump cylinder and processing technology
Technical Field
The invention belongs to the technical field of oil-well pumps in oil fields, and particularly relates to an amorphous nickel-tungsten-phosphorus alloy electroplating solution applied to electroplating of a pump cylinder of an oil-well pump and a processing technology thereof.
Background
The oil well pump mainly comprises a pump cylinder, a plunger, an oil inlet valve and an oil outlet valve. The oil pump is dragged by the oil pumping unit during working, and the plunger reciprocates up and down in the pump cylinder. During the upstroke, the oil outlet valve at the lower part of the plunger is closed, the plunger pushes crude oil in the pump barrel out of the pump barrel, meanwhile, the lower part of the plunger forms vacuum, and the oil is sucked into the pump barrel through the oil inlet valve. During the down stroke, the oil inlet valve is closed, oil is pressed to the upper side through the plunger and the oil outlet valve, and the oil is continuously pumped to the ground through continuous up-and-down movement. As most of the oil field development in China is carried out in the middle and later period, the development difficulty is increased, the medium of the oil well environment is continuously deteriorated, the well fluid contains corrosive media such as CO2, H2S, salt water and the like, and impurities such as sand grains and the like, and the oil well pump needs to work repeatedly for thousands of times every day in the severe environment, so that the oil well pump is required to have higher hardness, wear resistance, corrosion resistance and the like, and the requirements of field use are met. The pump barrel is the most important part of the oil well pump, and the value of the pump barrel accounts for more than 60% of the total value of the oil well pump. The primary failure modes of the pump barrel are wear and corrosion.
At present, the domestic pump cylinder inner wall treatment process mainly comprises chromium plating, nickel electroplating, chemical nickel phosphorus plating and the like. However, the above plating seeds have the disadvantages of serious environmental pollution, large brittleness, low electrodeposition speed, micro-cracks on the appearance, pinholes in the thick plating and the like. The corrosion resistance and the wear resistance can not meet the requirements of field use, and the large-scale popularization and use of the material are limited.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the amorphous nickel-tungsten-phosphorus alloy anti-corrosion and wear-resistant electroplating solution and the oil-well pump barrel electroplating processing technology, wherein the amorphous nickel-tungsten-phosphorus alloy anti-corrosion and wear-resistant electroplating solution has good corrosion resistance and wear resistance, and does not pollute the environment in the production process.
The invention provides an amorphous nickel-tungsten-phosphorus alloy electroplating solution applied to electroplating of a pump cylinder of an oil well pump, which adopts the technical scheme that: the composite material comprises main salt, a buffering agent, a complexing agent, conductive salt and deionized water, wherein the main salt comprises nickel sulfate, sodium tungstate and phosphorous acid, and the concentrations of the main salt, the sodium tungstate and the phosphorous acid are respectively 140g/L, 10-20g/L and 5-15 g/L; the buffer is boric acid, and the concentration of the boric acid is 25-35 g/L; the complexing agent is citric acid or sodium citrate, and the concentration of the complexing agent is 20-30 g/L; the conductive salt is sodium sulfate, and the concentration of the conductive salt is 20-30 g/L.
Further preferably, the concentrations of the nickel sulfate, the sodium tungstate and the phosphorous acid are 133g/L, 18g/L and 8 g/L; the concentration of the boric acid is 30g/L, and the concentration of the sodium sulfate is 24 g/L.
In a further improvement, additives are also added into the electroplating solution, and the additives can be two of the following:
firstly, the additive is modified silicon carbide, and the concentration of the additive is 5-8 g/L; the modified silicon carbide is obtained by the following steps: according to the weight ratio of 3-5: 4-5: 100-120: 3-6, mixing silicon carbide, deionized water, toluene and a silane coupling agent KH550, and stirring and reacting for 1-1.5 hours at 65-75 ℃; and after the reaction is finished, washing the solid product with acetone and deionized water in sequence, drying, and grinding until the average particle size is 20-50 nm to obtain the silicon carbide with the surface grafted with the silane coupling agent.
Secondly, the additive is modified composite silicon carbide, and the concentration of the additive is 4-6 g/L; the modified composite silicon carbide is obtained through the following steps: according to the weight ratio of 3-5: 2-4: 4-5: 100-120: 3-6, mixing silicon carbide, silicon nitride, deionized water, toluene and a silane coupling agent KH550, and stirring to react for 2-2.5 hours at 68-70 ℃; and after the reaction is finished, washing the solid product with acetone and deionized water in sequence, drying, and grinding until the average particle size is 20-50 nm to obtain the composite silicon carbide with the surface grafted with the silane coupling agent.
Furthermore, the two additives are subjected to surface positive charge treatment, and the treatment steps are as follows: silicon carbide (or composite silicon carbide) with a surface grafted with a silane coupling agent, acetonitrile, ionic liquid [ Hmim ] HSO4 and azobisisobutyronitrile according to a weight ratio of 5-8: 90-100: 3-5: 0.7-0.9, uniformly mixing in a nitrogen atmosphere, reacting for 5-6 hours at 82-86 ℃, washing the solid product with acetone and deionized water in sequence after the reaction is finished, drying, and grinding until the average particle size is 20-50 nm to obtain the silicon carbide (or composite silicon carbide) with positive charge on the surface.
The ionic liquid [ Hmim ] HSO4 is an existing ionic liquid, and can be prepared by the following steps: adding 8.2g of N-methylimidazole into a three-hole bottle with the capacity of 250mL, placing the three-hole bottle in an ice water bath, cooling to 0-5 ℃, adding 10-12 g of 98% (mass percent) concentrated sulfuric acid and 10mLH2O by using a rubber head dropper within 30min under vigorous stirring, and continuing stirring at room temperature for 2-4 h; after the reaction, the mixture was evaporated under reduced pressure at 75 ℃ to remove water, and the desired product [ Hmim ] HSO4 was obtained.
The second invention provides an electroplating processing technique of an oil well pump cylinder applying the amorphous nickel-tungsten-phosphorus alloy electroplating solution, wherein a processing workpiece is sequentially treated by the steps of electrolytic degreasing, electrochemical etching, activation, deionized water cleaning, electroplating and heat treatment, and the second invention is as follows:
the electrolytic degreasing is to treat in 65-75 ℃ degreasing liquid for 5-10 minutes, and the current density is controlled to be 5-10A/dm 2; the deoiling liquid is prepared from deoiling powder and water according to the mass ratio of 3-5: 100; the oil removing powder is prepared from NaOH, Na2CO3 and Na3PO4Prepared according to the mass ratio of 15-18:25-28:2-4, and the pH is kept between 10 and 13;
the electrochemical etching is to remove an oxide film in a sodium nitrate aqueous solution with the molar concentration of 0.4-0.5 mol/L, and the current density is controlled to be 5-10A/dm2;
The activation is to soak in a sulfuric acid solution with the concentration of 0.35-0.4M to increase the surface activity of the metal;
the electroplating adopts amorphous nickel-tungsten-phosphorus alloy electroplating solution, the pH value is adjusted to 2-3 by nickel carbonate, the electroplating temperature is more than or equal to 70 ℃, the current density is 5-10A/dm2, and the electroplating time is 3-4 hours; plating an amorphous nickel-tungsten-phosphorus anti-corrosion wear-resistant protective layer on the inner surface of the pump barrel through electroplating, wherein the thickness of the protective layer is not less than 75 mu m.
The heat treatment is heat preservation for 1-2 hours at the temperature of 300-400 ℃.
Further improvement, nano-rod-shaped AlOOH is added into the deoiling liquid, and the mass ratio of the nano-rod-shaped AlOOH to the deoiling powder is 1: 1-2; the preparation method of the nano-rod AlOOH comprises the following steps: preparing an aqueous solution containing 0.25g/L of hexadecyl trimethyl ammonium bromide (CTAB) and 0.14g/L of citric acid, uniformly dispersing by ultrasonic to obtain a composite soft template solution, adding 0.15mol/L of aluminum nitrate and 0.10mol/L of urea into the composite soft template solution, reacting for 2.5 hours at 80 ℃, naturally settling a white precipitate after the reaction is finished, centrifuging at 3000rpm for 7 minutes to remove a supernatant, and drying the bottom precipitate in vacuum to obtain the nano rod-shaped AlOOH.
In a further improvement, the soaking time in the activation is 30-60S.
Further improvement, the steps of electrolytic degreasing, electrochemical etching and electroplating are all provided with a water washing step.
The invention has the advantages that: the protective layer on the inner surface of the pump barrel adopts an amorphous nickel-tungsten-phosphorus alloy electroplating solution coating, and neutral salt spray resistance, acid-base corrosion resistance and sulfide resistance of the protective layer are improved by adjusting the component proportion of the electroplating solution; silicon carbide is added as an additive, so that the acid-base corrosion resistance and the wear resistance of the protective layer are improved; and through the modification treatment of the silicon carbide, the bonding performance of the silicon carbide, metal components and a matrix material is improved, the compactness of the structure is improved, and the acid-base corrosion resistance and the wear resistance of the protective layer are further improved.
Detailed Description
Example 1
An amorphous nickel-tungsten-phosphorus alloy electroplating solution applied to an electroplated layer of a pump cylinder of an oil well pump comprises main salt, a buffering agent, a complexing agent, conductive salt and deionized water, wherein the main salt comprises nickel sulfate, sodium tungstate and phosphorous acid, and the concentrations of the main salt, the conductive salt and the phosphorous acid are 120g/L, 20g/L and 10g/L respectively; the buffering agent is boric acid with the concentration of 25 g/L; the complexing agent is citric acid, and the concentration of the complexing agent is 20 g/L; the conductive salt was sodium sulfate, and the concentration was 30 g/L.
Example 2
An amorphous nickel-tungsten-phosphorus alloy electroplating solution applied to an electroplated layer of a pump cylinder of an oil well pump comprises main salt, a buffering agent, a complexing agent, conductive salt and deionized water, wherein the main salt comprises nickel sulfate, sodium tungstate and phosphorous acid, and the concentrations of the main salt, the nickel sulfate, the sodium tungstate and the phosphorous acid are respectively 140g/L, 15g/L and 15 g/L; the buffering agent is boric acid, and the concentration of the boric acid is 35 g/L; the complexing agent is sodium citrate, and the concentration of the complexing agent is 30 g/L; the conductive salt is sodium sulfate, and the concentration of the conductive salt is 20 g/L.
Example 3
An amorphous nickel-tungsten-phosphorus alloy electroplating solution applied to an electroplated layer of a pump cylinder of an oil well pump comprises main salt, a buffering agent, a complexing agent, conductive salt and deionized water, wherein the main salt comprises nickel sulfate, sodium tungstate and phosphorous acid, and the concentrations of the main salt, the nickel sulfate, the sodium tungstate and the phosphorous acid are 133g/L, 18g/L and 8g/L respectively; the buffering agent is boric acid with the concentration of 30 g/L; the complexing agent is prepared from citric acid and sodium citrate according to the mass ratio of 1:2, and the concentration of the complexing agent is 26 g/L; the conductive salt was sodium sulfate, which was present at a concentration of 24 g/L.
Example 4
An amorphous nickel-tungsten-phosphorus alloy electroplating solution applied to an electroplated layer of a pump cylinder of an oil well pump is prepared by adding an additive into the electroplating solution on the basis of embodiment 3, wherein the additive is silicon carbide with the average particle size of 25-35nm and the concentration of the silicon carbide is 6 g/L.
Example 5
An amorphous nickel-tungsten-phosphorus alloy electroplating solution applied to an electroplated layer of a pump cylinder of an oil well pump is prepared by adding an additive into the electroplating solution on the basis of embodiment 3, wherein the additive is modified silicon carbide and the concentration of the additive is 6 g/L; the modified silicon carbide is obtained by the following steps: according to the weight ratio of 4: 5: 110: 5, mixing silicon carbide, deionized water, toluene and a silane coupling agent KH550, and stirring and reacting for 1.5 hours at 65-75 ℃; and after the reaction is finished, washing the solid product with acetone and deionized water in sequence, drying, and grinding until the average particle size is 25-35nm to obtain the silicon carbide with the surface grafted with the silane coupling agent.
Example 6
An amorphous nickel-tungsten-phosphorus alloy electroplating solution applied to an electroplated layer of a pump cylinder of an oil well pump is prepared by adding an additive into the electroplating solution on the basis of embodiment 3, wherein the additive is modified composite silicon carbide and the concentration of the additive is 6 g/L; the modified composite silicon carbide is obtained by the following steps: according to the weight ratio of 4: 4: 5: 110: 5, mixing silicon carbide, silicon nitride, deionized water, toluene and a silane coupling agent KH550, and stirring and reacting for 2 hours at 68-70 ℃; and after the reaction is finished, washing the solid product with acetone and deionized water in sequence, drying, and grinding until the average particle size is 25-35nm to obtain the composite silicon carbide with the surface grafted with the silane coupling agent.
Example 7
The utility model provides an be applied to oil-well pump barrel electroplate layer's amorphous nickel tungsten phosphorus alloy plating solution, on embodiment 5's basis, the carborundum of surface grafting silane coupling agent still includes the positive charge treatment step of surface, and the treatment step is: silicon carbide with a surface grafted with a silane coupling agent, acetonitrile, ionic liquid [ Hmim ] HSO4 and azobisisobutyronitrile according to a weight ratio of 6: 100: 4: 0.8, uniformly mixing in a nitrogen atmosphere, reacting for 5 hours at 82-86 ℃, washing the solid product with acetone and deionized water in sequence after the reaction is finished, drying, and grinding until the average particle size is 25-35nm to obtain the silicon carbide with positive charge on the surface.
Example 8
The utility model provides an be applied to oil-well pump barrel electroplate layer's amorphous state nickel tungsten phosphorus alloy plating solution, on embodiment 6 basis, compound carborundum of surface grafting silane coupling agent still includes the positive charged treatment step of surface, and the treatment step is: the preparation method comprises the following steps of (1) grafting composite silicon carbide with a silane coupling agent grafted on the surface, acetonitrile, ionic liquid [ Hmim ] HSO4 and azobisisobutyronitrile according to the weight ratio of 6: 100: 4: 0.8, uniformly mixing in a nitrogen atmosphere, reacting for 5 hours at 82-86 ℃, washing solid products with acetone and deionized water in sequence after the reaction is finished, drying, and grinding until the average particle size is 25-35nm to obtain the composite silicon carbide with positively-charged surface.
Example 9
An electroplating process for oil-well pump cylinders by using the amorphous nickel-tungsten-phosphorus alloy electroplating solution comprises the following steps of electrolytic degreasing, electrochemical etching, activation, deionized water cleaning, electroplating and heat treatment of a processed workpiece in sequence:
electrolytic degreasing is carried out by treating in degreasing liquid at 68-70 deg.C for 10 min, and controlling current density at 5-10A/dm2(ii) a The deoiling liquid is prepared from deoiling powder and water according to the mass ratio of 5: 100; the oil removing powder is prepared from NaOH and Na2CO3 and Na3PO4Prepared according to the mass ratio of 15-18:25-28:2-4, and the pH is kept between 10 and 13;
the electrochemical etching is carried out in sodium nitrate aqueous solution with the molar concentration of 0.5mol/LTreating to remove oxide film, and controlling current density to 5-10A/dm2;
The activation is to soak 60S in a sulfuric acid solution with the concentration of 0.4M so as to increase the surface activity of the metal;
electroplating with the amorphous nickel-tungsten-phosphorus alloy electroplating solutions obtained in examples 1-8, respectively, and adjusting the pH value to 2-3 with nickel carbonate at 75 deg.C and a current density of 5-10A/dm2 for 3 hours; an amorphous nickel-tungsten-phosphorus anti-corrosion wear-resistant protective layer is plated on the inner surface of the pump barrel through electroplating, and the thickness of the protective layer is 85 micrometers.
The heat treatment is carried out at 350 ℃ for 1.5 hours.
The steps of electrolytic degreasing, electrochemical etching and electroplating are all followed by a water washing step and a deionized water washing step in the steps, and the purpose of the steps is to wash workpieces and remove residual liquid in the previous step.
The obtained amorphous nickel-tungsten-phosphorus anticorrosive wear-resistant protective layer and protective layers obtained by conventional nickel electroplating and chemical nickel-phosphorus electroplating are respectively subjected to the following experiments, and the average experimental data are as follows:
first, the test result of neutral salt spray, acid and alkaline resistance of the protective coating in the pump barrel
By the comparison, it can be seen that the nickel-tungsten-phosphorus coatings obtained from the electroplating solutions in examples 1-8 have no change in the neutral salt spray experiment for 300h, no change in the nickel-tungsten-phosphorus coatings obtained from the electroplating solutions after being soaked in 5% sulfuric acid solution for 300h, and no change in the nickel-tungsten-phosphorus coatings obtained from the electroplating solutions in examples 5-8 in the neutral salt spray experiment2The S solution is not changed after being soaked for 300h, and the 5 percent NaOH alkaline solution is not changed after being soaked for 300 h. Through the experimental data, compared with the conventional electroplating or chemical plating protective layer, the protective layer obtained by the electroplating solution formula and the electroplating process has better acid and alkali resistance. And tests prove that the time from the beginning of the test to the slight color change of the coating of the protective layer obtained in the embodiment 2-8 is sequentially prolonged and basically changes in a gradient way, and the concrete steps are as follows:
second, the wear resistance comparison data of the protective coating in the pump barrel
Through the comparison, the nickel-tungsten-phosphorus coating is obtained from the electroplating solution in the examples 1-8, and through a grinding comparison experiment, the average abrasion loss of the nickel-tungsten-phosphorus pump cylinder is smaller than that of other processes; and tests prove that the wear resistance of the protective layer of the pump barrel obtained in the embodiments 1 to 8 basically shows an ascending trend, which is specifically as follows:
through the two experiments, the addition of the silicon carbide and the composite silicon carbide can improve the acid-base corrosion resistance and the wear resistance of the coating to a certain extent; and after the silicon carbide and the composite silicon carbide are modified, the bonding performance of the silicon carbide and the metal components in the coating and the base material can be improved, so that the acid-base corrosion resistance and the wear resistance of the coating are further improved.
Example 10
Nano rod-shaped AlOOH is also added into the deoiling liquid in the embodiment 9, and the mass ratio of the nano rod-shaped AlOOH to the deoiling powder is 1: 1.5; the preparation method of the nano-rod AlOOH comprises the following steps: preparing an aqueous solution containing 0.25g/L of hexadecyl trimethyl ammonium bromide (CTAB) and 0.14g/L of citric acid, uniformly dispersing by ultrasonic to obtain a composite soft template solution, adding 0.15mol/L of aluminum nitrate and 0.10mol/L of urea into the composite soft template solution, reacting for 2.5 hours at 80 ℃, naturally settling a white precipitate after the reaction is finished, centrifuging at 3000rpm for 7 minutes to remove a supernatant, and drying the bottom precipitate in vacuum to obtain the nano rod-shaped AlOOH.
On the basis that the steps of electrolytic degreasing are consistent with those of the embodiment, the same effect as that of degreasing for 10 minutes in the embodiment 9 can be obtained by treating the degreased liquid at 68-70 ℃ for 5 minutes, and the cleaning efficiency is doubled. Namely, the nano-rod AlOOH is added to destroy the bonding structure between the oil and the workpiece through impact, so that the oil can be favorably separated from the surface of the workpiece; and meanwhile, the oil absorption performance is realized, and the further contact between oil and a workpiece is reduced. Meanwhile, according to the technical index of the oil well pump cylinder obtained after electroplating processing, the technical index of the pump cylinder is not negatively influenced.
The above description is only exemplary of the present invention, and those skilled in the art may modify the present invention or modify the present invention into equivalent technical solutions by using the technical solutions described above. Therefore, any simple modifications or equivalent substitutions made in accordance with the technical solution of the present invention are within the scope of the claims of the present invention.