CN111204807B - Preparation method of high-solubility molybdenum trioxide for nickel-molybdenum-phosphorus petroleum hydrodesulfurization catalyst - Google Patents

Preparation method of high-solubility molybdenum trioxide for nickel-molybdenum-phosphorus petroleum hydrodesulfurization catalyst Download PDF

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CN111204807B
CN111204807B CN202010042271.9A CN202010042271A CN111204807B CN 111204807 B CN111204807 B CN 111204807B CN 202010042271 A CN202010042271 A CN 202010042271A CN 111204807 B CN111204807 B CN 111204807B
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CN111204807A (en
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牛海涛
张惠
杜家森
谭刚
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Liaoning Tianqiao New Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C01G39/02—Oxides; Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P

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Abstract

A preparation method of high-solubility molybdenum trioxide for a nickel-molybdenum-phosphorus petroleum hydrodesulfurization catalyst comprises the steps of drying ammonium molybdate, feeding the ammonium molybdate into a kiln head of an electric heating rotary furnace from a kiln head closed bin through a double-screw feeder, moving the ammonium molybdate from the kiln head to a kiln tail, feeding the ammonium molybdate into a kiln tail bin, feeding the ammonium molybdate into a screening machine, and sieving the ammonium molybdate through a 60-mesh sieve, wherein the electric heating rotary furnace is divided into four temperature zones, and the lengths of the temperature zones are the same; uniformly distributing the screened materials to a stainless steel mesh belt of an electric heating mesh belt furnace through a distributor for roasting, wherein the electric heating mesh belt furnace is divided into five temperature zones, the retention time of the materials in the electric heating mesh belt furnace is 3.0h-4.0h, a screening machine is connected to the discharge end of the electric heating mesh belt furnace, sieving is carried out by a 60-mesh sieve, and then the materials are mixed to obtain the product. The advantages are that: the high-solubility molybdenum trioxide has the purity of more than or equal to 99.95 percent, has ultrahigh solubility in a high-concentration nickel-molybdenum-phosphorus catalyst system, has the solubility of more than or equal to 99.999 percent, and meets the special requirement of molybdenum-containing catalyst manufacturers on the solubility of high-purity molybdenum trioxide.

Description

Preparation method of high-solubility molybdenum trioxide for nickel-molybdenum-phosphorus petroleum hydrodesulfurization catalyst
Technical Field
The invention relates to a preparation method of high-solubility molybdenum trioxide for a nickel-molybdenum-phosphorus petroleum hydrodesulfurization catalyst.
Background
With the continuous strengthening of the national protection force on the atmospheric environment, the requirement on the sulfur content in the finished oil is more and more strict, and the requirement allowable content is lower and lower, so that the consumption of molybdenum-containing catalysts for hydrodesulfurization and the like for improving the quality of the finished oil is greatly increased, the yield of the catalysts is increased on one hand for adapting to the change of molybdenum-containing catalyst manufacturers, and on the other hand, the formula of the catalysts is continuously improved and optimized, and the activity and the service life of the catalysts are continuously improved.
The molybdenum-containing catalyst has various purposes, including cobalt-molybdenum hydrodesulfurization catalyst, nickel-molybdenum catalyst, ruthenium-molybdenum catalyst, iron-nickel-chromium-molybdenum catalyst, nickel-molybdenum-chromium catalyst, cobalt-molybdenum-phosphorus catalyst, nickel-molybdenum-phosphorus catalyst, and the like, and the solubility requirements of different catalysts on one of raw materials used for producing the high-purity molybdenum trioxide are different and higher.
In recent years, some manufacturers of nickel-molybdenum-phosphorus hydrodesulfurization catalysts have increasingly high requirements on the solubility of high-purity molybdenum trioxide, and the content of the high-purity molybdenum trioxide in a nickel-molybdenum-phosphorus solution system reaches a very high value which is about 14 times of the content of the high-purity molybdenum trioxide before several years. In 2013, 11g-12g of molybdenum trioxide is required to be dissolved in 150mL of water for a nickel-molybdenum-phosphorus petroleum hydrodesulfurization catalyst system, along with the progress of the catalyst industry, the requirement on the content of the molybdenum trioxide in the nickel-molybdenum-phosphorus petroleum hydrodesulfurization catalyst system is higher and higher, in 2018, 90-100g of molybdenum trioxide is required to be dissolved in 100mL of water for the nickel-molybdenum-phosphorus petroleum hydrodesulfurization catalyst system, the catalyst of the system can be called as a novel hydrodesulfurization catalyst, straight-run fuel oil S produced by using the catalyst is less than or equal to 10mg/kg, and the harsh environment-friendly requirement is met, however, the solubility of the molybdenum trioxide in the nickel-molybdenum-phosphorus catalyst system is greatly improved, and the original solubility of the molybdenum trioxide does not meet the requirement of the existing system.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of high-purity high-solubility molybdenum trioxide for a nickel-molybdenum-phosphorus petroleum hydrodesulfurization catalyst, which meets the strict solubility index requirement in a high-concentration nickel-molybdenum-phosphorus catalyst system.
The technical scheme of the invention is as follows:
a preparation method of high-solubility molybdenum trioxide for a nickel-molybdenum-phosphorus petroleum hydrodesulfurization catalyst comprises the following specific steps:
(1) drying ammonium molybdate for later use; the purity of the ammonium molybdate is more than or equal to 99.95 percent, wherein the Mo content is 56-58 percent, the K content is less than 60ppm, and the total content of Fe and Pb is less than 50 ppm; cl is less than 20 ppm;
(2) the material ammonium molybdate is sent into the kiln head of the electric heating rotary furnace from a kiln head closed stock bin through a double-screw feeder, moves from the kiln head to the kiln tail, is discharged from the kiln tail to enter a kiln tail stock bin, then enters a sieving machine, is sieved by a sieve of 60 meshes, and is sent to an electric heating mesh belt furnace;
the electric heating rotary furnace is divided into four sections of temperature zones, the length of each section of temperature zone is the same, the temperature of the first section of temperature zone of the electric heating rotary furnace is t1, the temperature of the second section of temperature zone is t2 ═ t1+25 ℃, the temperature of the third section of temperature zone is t3 ═ t2+35 ℃, and the temperature of the four section of temperature zone is t4 ═ t1-20 ℃; wherein, t1 is 510-550 ℃;
the rotating speed of the electric heating rotary furnace body is 1.0rpm-2.0 rpm; the feeding speed is 100kg/h-200 kg/h; the inclination angle of the kiln body is 0.5-1 degrees, and the materials are in the electric heating rotary furnaceThe retention time of the catalyst is 1.5h-2.5 h; the furnace end of the electric heating rotary furnace is connected with a negative pressure fan through a pipeline, and the air induction quantity of the negative pressure fan is 500m 3 /h-800m 3 /h；
(3) Uniformly distributing the screened materials to a stainless steel mesh belt of an electric heating mesh belt furnace through a distributor, wherein the electric heating mesh belt furnace is divided into five temperature zones, the length of each temperature zone is the same, and the temperature of the five temperature zones is 460 ℃, 470 ℃, 480 ℃, 490 ℃ and 500 ℃ from front to back; the transmission speed of the stainless steel mesh belt is 60mm/min-100mm/min, the thickness of the material layer is 20mm-40mm, and the retention time of the materials in the electric heating mesh belt furnace is 3.0h-4.0 h; an induced draft port is arranged on the mesh belt furnace body, the induced draft port is connected with a negative pressure fan through a pipeline, and the induced draft of the negative pressure air quantity is 800m 3 /h-1500m 3 /h；
(4) And (3) connecting a screening machine at the discharge end of the electric heating mesh belt furnace, screening by a 60-mesh sieve, mixing materials by a cantilever double-cone spiral mixer for 2-4 h to obtain the high-solubility molybdenum trioxide for the nickel-molybdenum-phosphorus petroleum hydrodesulfurization catalyst.
Further, the thickness of the ammonium molybdate rotary material layer in the electric heating rotary furnace is 150mm-250 mm.
Further, the ammonium molybdate is ammonium dimolybdate or ammonium tetramolybdate, wherein after the drying in the step (1), the mass content of the water in the ammonium tetramolybdate is less than 6.0%, and the mass content of the water in the ammonium dimolybdate is less than 0.3%.
Further, when the ammonium molybdate is ammonium tetramolybdate, the temperature of the electric heating rotary furnace is t 1-510-530 ℃.
Further, when the ammonium molybdate is ammonium dimolybdate, the temperature of the electric heating rotary furnace is t 1-540-550 ℃.
The invention has the beneficial effects that:
the K content in the raw materials is strictly controlled, so that the solubility of the final product is ensured; the contents of K, Fe, Pb and Cl are strictly controlled, and the quality standard requirement of the molybdenum trioxide for the catalyst is met. The electrothermal rotary furnace is a four-temperature-zone dynamic roasting decomposition, and the electrothermal mesh belt furnace is a five-temperature-zone static roasting decomposition. Roasting the molybdenum trioxide by a first-stage rotary furnace to obtain a roasted product, namely a molybdenum trioxide neutral phase (NH) 4 ) 2 Mo 22 O 67 The content is a little higher than that of the traditional Chinese medicine,cannot be easily and precisely controlled, at the moment, NH in molybdenum trioxide 4 The content is 30-50ppm, the mixture is further accurately roasted and decomposed in an electric heating mesh belt furnace, the temperature control of the electric heating mesh belt furnace is more accurate, and the obtained roasted and decomposed product molybdenum trioxide phase (NH) 4 ) 2 Mo 22 O 67 The content is reduced when NH in the molybdenum trioxide 4 The content is reduced to 10-15ppm, the solubility is the best at the moment and can reach 99.999 percent, the high-solubility molybdenum trioxide has the purity of more than or equal to 99.95 percent, and the high-solubility molybdenum trioxide has ultrahigh solubility in a high-concentration nickel-molybdenum-phosphorus catalyst system, thereby meeting the special requirement of molybdenum-containing catalyst manufacturers on the solubility of the high-purity molybdenum trioxide.
Detailed Description
Example 1
(1) Drying ammonium dimolybdate until the water content is less than 0.3% by mass for later use; the purity of the ammonium dimolybdate is more than or equal to 99.95 percent, wherein the Mo content is 56-58 percent, the K content is less than 60ppm, and the total content of Fe and Pb is less than 50 ppm; cl is less than 20 ppm;
(2) feeding ammonium dimolybdate into a kiln head of an electric heating rotary furnace from a kiln head closed bin through a double-screw feeder, moving from the kiln head to a kiln tail, feeding the kiln tail into a kiln tail bin, then feeding the kiln tail into a screening machine, screening through a 60-mesh sieve, and feeding undersize materials into an electric heating mesh belt furnace through a material lifting hopper;
the electric heating rotary furnace (hot zone phi 800mm multiplied by 6000mm) is divided into four sections of temperature zones, the length of each section of temperature zone is the same, the temperature of one section of temperature zone of the electric heating rotary furnace is t 1-540 ℃, the temperature of the two section of temperature zone is t 2-t 1+25 ℃ -565 ℃, the temperature of the three section of temperature zone is t 3-t 2+35 ℃ -600 ℃, and the temperature of the four section of temperature zone is t 4-t 1-20 ℃ 580 ℃;
the rotating speed of the furnace body of the electric heating rotary furnace is 1.0 rpm; the feeding speed is 100 kg/h; the thickness of the ammonium molybdate rotary material layer in the electric heating rotary furnace is 150 mm; the inclination angle of the kiln body is 0.5 degrees, and the retention time of the materials in the electric heating rotary furnace is 2.5 hours; the furnace end of the electric heating rotary furnace is connected with a negative pressure fan through a pipeline, and the air induction quantity of the negative pressure fan is 500m 3 /h；
(3) Uniformly distributing the screened material onto a stainless steel mesh belt of an electric heating mesh belt furnace through a distributor, wherein the width of the stainless steel mesh belt is 1000mm, the electric heating mesh belt furnace is divided into five temperature zones, the length of each temperature zone is the same, and the temperature of the five temperature zones is from front to backThen 460 ℃, 470 ℃, 480 ℃, 490 ℃ and 500 ℃ are carried out in sequence; the transmission speed of the stainless steel mesh belt is 60mm/min, the thickness of the material layer is 40mm, and the retention time of the materials in the electric heating mesh belt furnace is 4 h; an induced draft port is arranged on the mesh belt furnace body, the induced draft port is connected with a negative pressure fan through a pipeline, and the induced draft of the negative pressure draft is 1500m 3 /h；
(4) And connecting a screening machine at the discharge end of the electric heating mesh belt furnace, screening through a 60-mesh sieve, mixing the undersize materials through a cantilever double-cone spiral mixer for 2 hours to obtain the high-solubility molybdenum trioxide with the purity of more than or equal to 99.95 percent for the gray green nickel-molybdenum-phosphorus petroleum hydrodesulfurization catalyst.
Example 2
(1) Drying ammonium dimolybdate until the water content is less than 0.3% by mass for later use; the purity of the ammonium dimolybdate is more than or equal to 99.95 percent, wherein the Mo content is 56-58 percent, the K content is less than 60ppm, and the total content of Fe and Pb is less than 50 ppm; cl is less than 20 ppm;
(2) feeding ammonium dimolybdate into a kiln head of an electric heating rotary furnace from a kiln head closed bin through a double-screw feeder, moving from the kiln head to a kiln tail, feeding the kiln tail into a kiln tail bin, then feeding the kiln tail into a screening machine, screening through a 60-mesh sieve, and feeding undersize materials into an electric heating mesh belt furnace through a material lifting hopper;
the electric heating rotary furnace (hot zone phi 800mm multiplied by 6000mm) is divided into four sections of temperature zones, the length of each section of temperature zone is the same, the temperature of one section of temperature zone of the electric heating rotary furnace is t 1-550 ℃, the temperature of the two section of temperature zone is t 2-t 1+25 ℃ 575 ℃, the temperature of the three section of temperature zone is t 3-t 2+35 ℃ 610 ℃, and the temperature of the four section of temperature zone is t 4-t 1-20 ℃ 590 ℃;
the rotating speed of the furnace body of the electric heating rotary furnace is 2.0 rpm; the feeding speed is 200 kg/h; the thickness of an ammonium molybdate rotary material layer in the electric heating rotary furnace is 250 mm; the inclination angle of the kiln body is 1 degree, and the staying time of the materials in the electric heating rotary furnace is 1.5 h; the furnace end of the electric heating rotary furnace is connected with a negative pressure fan through a pipeline, and the air induction quantity of the negative pressure fan is 800m 3 /h；
(3) Uniformly distributing the screened materials on a stainless steel mesh belt of an electric heating mesh belt furnace through a distributor, wherein the width of the stainless steel mesh belt is 1000mm, the electric heating mesh belt furnace is divided into five sections of temperature zones, the lengths of the temperature zones of the five sections are the same, and the temperatures of the five sections of temperature zones are 460 ℃, 470 ℃ and 480 ℃ from front to back in sequence490 ℃ and 500 ℃; the transmission speed of the stainless steel mesh belt is 100mm/min, the thickness of the material layer is 20mm, and the retention time of the material in the electric heating mesh belt furnace is 3 h; an induced draft port is arranged on the mesh belt furnace body, the induced draft port is connected with a negative pressure fan through a pipeline, and the induced draft of the negative pressure air quantity is 800m 3 /h；
(4) And (3) connecting a screening machine at the discharge end of the electric heating mesh belt furnace, screening by a 60-mesh sieve, mixing the undersize materials by a cantilever double-cone spiral mixer for 4 hours to obtain the high-solubility molybdenum trioxide with the purity of more than or equal to 99.95 percent for the gray green nickel-molybdenum-phosphorus petroleum hydrodesulfurization catalyst.
Example 3
(1) Drying ammonium tetramolybdate until the water content is less than 6.0% by mass for later use; the purity of the ammonium tetramolybdate is more than or equal to 99.95 percent, wherein the Mo content is 56-58 percent, the K content is less than 60ppm, and the total content of Fe and Pb is less than 50 ppm; cl is less than 20 ppm;
(2) the material ammonium tetramolybdate is fed into the kiln head of the electric heating rotary furnace from the kiln head closed bin through a double-screw feeder, moves from the kiln head to the kiln tail, discharges materials from the kiln tail to enter the kiln tail bin, then enters a sieving machine, is sieved by a 60-mesh sieve, and the undersize materials are fed into the electric heating mesh belt furnace through a material-lifting hopper;
the electric heating rotary furnace (hot zone phi 800mm multiplied by 6000mm) is divided into four sections of temperature zones, the length of each section of temperature zone is the same, the temperature of one section of temperature zone of the electric heating rotary furnace is t1 ═ 510 ℃, the temperature of the two section of temperature zone is t2 ═ t1+25 ℃:, the temperature of the three section of temperature zone is t3 ═ t2+35 ℃:, and the temperature of the four sections of temperature zone is t4 ═ t1-20 ℃;
the rotating speed of the furnace body of the electric heating rotary furnace is 1.5 rpm; the feeding speed is 150 kg/h; the thickness of the ammonium molybdate rotary material layer in the electric heating rotary furnace is 200 mm; the inclination angle of the kiln body is 0.6 degrees, and the retention time of the materials in the electric heating rotary furnace is 2.0 hours; the furnace end of the electric heating rotary furnace is connected with a negative pressure fan through a pipeline, and the air induction quantity of the negative pressure fan is 600m 3 /h；
(3) Uniformly distributing the screened materials onto a stainless steel mesh belt of an electric heating mesh belt furnace through a distributor, wherein the width of the stainless steel mesh belt is 1000mm, the electric heating mesh belt furnace is divided into five temperature zones, the length of each temperature zone is the same, and the temperature of the five temperature zones is 460 ℃, 470 ℃, 480 ℃, 490 ℃ and 500 ℃ from front to back; stainless steel netThe belt transmission speed is 80mm/min, the material layer thickness is 30mm, and the retention time of the materials in the electric heating belt furnace is 3.5 h; an induced draft port is arranged on the furnace body of the mesh belt furnace, the induced draft port is connected with a negative pressure fan through a pipeline, and the induced draft of the negative pressure air quantity is 1000m 3 /h；
(4) And connecting a screening machine at the discharge end of the electric heating mesh belt furnace, screening by a 60-mesh sieve, mixing the undersize materials by a cantilever double-cone spiral mixer for 4 hours to obtain the high-solubility molybdenum trioxide with the purity of more than or equal to 99.95 percent for the gray green nickel-molybdenum-phosphorus petroleum hydrodesulfurization catalyst.
Example 4
(1) Drying ammonium tetramolybdate until the water content is less than 6.0% by mass for later use; the purity of the ammonium tetramolybdate is more than or equal to 99.95 percent, wherein the Mo content is 56-58 percent, the K content is less than 60ppm, and the total content of Fe and Pb is less than 50 ppm; cl is less than 20 ppm;
(2) the material ammonium tetramolybdate is fed into the kiln head of the electric heating rotary furnace from the kiln head closed bin through a double-screw feeder, moves from the kiln head to the kiln tail, discharges materials from the kiln tail to enter the kiln tail bin, then enters a sieving machine, is sieved by a 60-mesh sieve, and the undersize materials are fed into the electric heating mesh belt furnace through a material-lifting hopper;
the electric heating rotary furnace (hot zone phi 800mm multiplied by 6000mm) is divided into four sections of temperature zones, the length of each section of temperature zone is the same, the temperature of one section of temperature zone of the electric heating rotary furnace is t 1-530 ℃, the temperature of the two section of temperature zone is t 2-t 1+25 ℃ and 555 ℃, the temperature of the three section of temperature zone is t 3-t 2+35 ℃ and 590 ℃, and the temperature of the four section of temperature zone is t 4-t 1-20 ℃ and 570 ℃;
the rotating speed of the electric heating rotary furnace body is 1.8 rpm; the feeding speed is 180 kg/h; the thickness of an ammonium molybdate rotary material layer in the electric heating rotary furnace is 180 mm; the inclination angle of the kiln body is 0.8 degrees, and the retention time of the materials in the electric heating rotary furnace is 1.8 hours; the furnace end of the electric heating rotary furnace is connected with a negative pressure fan through a pipeline, and the air induction quantity of the negative pressure fan is 750m 3 /h；
(3) Uniformly distributing the screened materials onto a stainless steel mesh belt of an electric heating mesh belt furnace through a distributor, wherein the width of the stainless steel mesh belt is 1000mm, the electric heating mesh belt furnace is divided into five temperature zones, the lengths of the temperature zones of the five sections are the same, and the temperatures of the five temperature zones are 460 ℃, 470 ℃, 480 ℃, 490 ℃ and 500 ℃ from front to back; the transmission speed of the stainless steel mesh belt is 90mm/min, and the material isThe thickness of the layer is 32mm, and the staying time of the material in the electric heating mesh belt furnace is 3.5 h; an induced draft port is arranged on the furnace body of the mesh belt furnace, the induced draft port is connected with a negative pressure fan through a pipeline, and the induced draft of the negative pressure air quantity is 900m 3 /h；
(4) And (2) connecting a screening machine at the discharge end of the electric heating mesh belt furnace, screening by a 60-mesh sieve, mixing the undersize materials by a cantilever double-cone spiral mixer for 2 hours to obtain the high-solubility molybdenum trioxide with the purity of more than or equal to 99.95 percent for the grayish green nickel-molybdenum-phosphorus petroleum hydrodesulfurization catalyst.
Comparative example 1
(1) Drying ammonium tetramolybdate until the water content is less than 6.0% by mass for later use; the purity of the ammonium tetramolybdate is more than or equal to 99.95 percent, wherein the Mo content is 56-58 percent, the K content is less than 60ppm, and the total content of Fe and Pb is less than 50 ppm; cl is less than 20 ppm;
(2) the material ammonium tetramolybdate is fed into the kiln head of the electric heating rotary furnace from the kiln head closed bin through a double-screw feeder, moves from the kiln head to the kiln tail, discharges materials from the kiln tail into the kiln tail bin, then enters a sieving machine, is sieved by a 40-mesh sieve, and the undersize materials are fed into the electric heating mesh belt furnace through a material-lifting hopper;
the electric heating rotary furnace (hot zone phi 800mm multiplied by 6000mm) is divided into four sections of temperature zones, the length of each section of temperature zone is the same, the temperature of one section of temperature zone of the electric heating rotary furnace is t 1-530 ℃, the temperature of the two section of temperature zone is t 2-t 1+25 ℃ and 555 ℃, the temperature of the three section of temperature zone is t 3-t 2+35 ℃ and 590 ℃, and the temperature of the four section of temperature zone is t 4-t 1-20 ℃ and 570 ℃; sieving the obtained molybdenum trioxide by a 40-mesh sieve;
the rotating speed of the furnace body of the electric heating rotary furnace is 1.8 rpm; the feeding speed is 180 kg/h; the thickness of an ammonium molybdate rotary material layer in the electric heating rotary furnace is 180 mm; the inclination angle of the kiln body is 0.8 degrees, and the retention time of the materials in the electric heating rotary furnace is 1.8 hours; the furnace end of the electric heating rotary furnace is connected with a negative pressure fan through a pipeline, and the air induction quantity of the negative pressure fan is 750m 3 /h。
Solubility test
100g of catalyst is dissolved by molybdenum trioxide, 32g of basic nickel carbonate, 18.5g of phosphoric acid and 100mL of pure water under stirring by a magnetic stirrer at 95 ℃ for 1 hour, and is filtered, observed and analyzed (2018 catalyst factory solubility detection method).
TABLE 1 tables of results of measuring solubility and ammonia content in examples of the present invention and comparative examples
Figure BDA0002368175490000081
Examples 1-4 high-soluble molybdenum trioxide (100 g), insoluble substances in a 14-time nickel-molybdenum-phosphorus catalyst system are less than 1mg, the dissolution rate is more than or equal to 99.999%, and the solution is dark green, transparent and meets the requirements of catalyst manufacturers.
Calcining in a section of electric heating rotary furnace to obtain a molybdenum trioxide mesomorphic phase (NH) as a calcining product 4 ) 2 Mo 22 O 67 The content is slightly high, and the accurate control is not easy, so that NH in the molybdenum trioxide in the examples 1, 2, 3 and 4 4 The content is 38ppm, 50ppm, 30ppm and 42ppm, the product meets the quality requirement of a detection method of a catalyst factory in 2013, and the solubility is 99.99% according to a solubility test in 2013; the product is further precisely roasted and decomposed in a mesh belt furnace, and the roasted and decomposed product molybdenum trioxide mesomorphic phase (NH) 4 ) 2 Mo 22 O 67 The content is reduced to 10ppm-15ppm, the solubility is the best at the moment, the solubility can reach 99.999 percent according to the detection method of the solubility of a catalyst factory in 2018, and the catalyst has ultrahigh solubility in a high-concentration system. The detection method of the catalyst factory in 2013 comprises the following steps: 11g of catalyst is dissolved for 30min by molybdenum trioxide +3.5g of basic nickel carbonate +2g of phosphoric acid +150mL of pure water with stirring of a magnetic stirrer, and the solution is filtered, observed, analyzed, filtered and analyzed.
The method controls the roasting degree by reasonably controlling the roasting temperature and the roasting time, so as to obtain the high-solubility molybdenum trioxide. If the molybdenum trioxide obtained by over-roasting (high temperature and long time) is pure molybdenum trioxide (complete MoO) with partial yellow color 3 In which NH 4 The content is substantially zero), its solubility is poor. And the catalyst is gray or grey-green by using molybdenum trioxide.
The above description is only exemplary of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (2)

1. A preparation method of high-solubility molybdenum trioxide for a nickel-molybdenum-phosphorus petroleum hydrodesulfurization catalyst is characterized by comprising the following steps:
the method comprises the following specific steps:
(1) drying ammonium molybdate for later use; the purity of the ammonium molybdate is more than or equal to 99.95 percent, wherein the Mo content is 56-58 percent, the K content is less than 60ppm, and the total content of Fe and Pb is less than 50 ppm; cl is less than 20 ppm;
(2) the material ammonium molybdate is sent into the kiln head of the electric heating rotary furnace from a kiln head closed stock bin through a double-screw feeder, moves from the kiln head to the kiln tail, the kiln tail is discharged and enters a kiln tail stock bin, then enters a sieving machine, is sieved by a sieve with 60 meshes, and the undersize is sent to an electric heating mesh belt furnace from a material lifting hopper;
the electric heating rotary furnace is divided into four sections of temperature zones, the length of each section of temperature zone is the same, the temperature of the first section of temperature zone of the electric heating rotary furnace is t1, the temperature of the second section of temperature zone is t2 ═ t1+25 ℃, the temperature of the third section of temperature zone is t3 ═ t2+35 ℃, and the temperature of the fourth section of temperature zone is t4 ═ t1-20 ℃; wherein, t1 is 510-550 ℃; the rotating speed of the electric heating rotary furnace body is 1.0rpm-2.0 rpm; the feeding speed is 100kg/h-200 kg/h; the inclination angle of the kiln body is 0.5-1 DEG, and the retention time of the materials in the electric heating rotary furnace is 1.5-2.5 h; the furnace end of the electric heating rotary furnace is connected with a negative pressure fan through a pipeline, and the air induction quantity of the negative pressure fan is 500m 3 /h-800m 3 /h；
(3) Uniformly distributing the screened materials to a stainless steel mesh belt of an electric heating mesh belt furnace through a distributor, wherein the electric heating mesh belt furnace is divided into five temperature zones, the length of each temperature zone is the same, and the temperature of the five temperature zones is 460 ℃, 470 ℃, 480 ℃, 490 ℃ and 500 ℃ from front to back; the transmission speed of the stainless steel mesh belt is 60mm/min-100mm/min, the thickness of the material layer is 20mm-40mm, and the retention time of the material in the electric heating mesh belt furnace is 3h-4 h; an induced draft port is arranged on the mesh belt furnace body, the induced draft port is connected with a negative pressure fan through a pipeline, and the induced draft of the negative pressure air quantity is 800m 3 /h-1500m 3 /h；
(4) Connecting a screening machine at the discharge end of the electric heating mesh belt furnace, screening by a 60-mesh sieve, mixing materials by a cantilever double-cone spiral mixer for 2-4 hours to obtain the high-solubility molybdenum trioxide for the nickel-molybdenum-phosphorus petroleum hydrodesulfurization catalyst;
the ammonium molybdate is ammonium dimolybdate or ammonium tetramolybdate, wherein after the drying in the step (1), the mass content of water in the ammonium tetramolybdate is less than 6.0%, and the mass content of water in the ammonium dimolybdate is less than 0.3%;
when the ammonium molybdate is ammonium tetramolybdate, a first temperature zone of the electric heating rotary furnace is t 1-510-530 ℃;
when the ammonium molybdate is ammonium dimolybdate, the temperature of a first section of the electric heating rotary furnace is t 1-540-550 ℃.
2. The method for preparing the highly soluble molybdenum trioxide for the nickel-molybdenum-phosphorus petroleum hydrodesulfurization catalyst as claimed in claim 1, which is characterized by comprising the following steps: the thickness of the ammonium molybdate rotary material layer in the electric heating rotary furnace is 150mm-250 mm.
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