CN109456796A - A kind of preparation method of the high boiling aromatic hydrocarbon solvent for insecticide emulsion - Google Patents

A kind of preparation method of the high boiling aromatic hydrocarbon solvent for insecticide emulsion Download PDF

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CN109456796A
CN109456796A CN201811382709.7A CN201811382709A CN109456796A CN 109456796 A CN109456796 A CN 109456796A CN 201811382709 A CN201811382709 A CN 201811382709A CN 109456796 A CN109456796 A CN 109456796A
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high boiling
hydrocarbon solvent
aromatic hydrocarbon
preparation
boiling aromatic
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谈勇
谈俊
江晓龙
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Peng East Materials Polytron Technologies Inc
Pengchen New Material Technology Co Ltd
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    • 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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Materials Engineering (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Toxicology (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses a kind of preparation methods of high boiling aromatic hydrocarbon solvent for insecticide emulsion, this method is specifically includes the following steps: be made porous carrier using corn stover, flyash, paper pulp mud, nano-titanium oxide, clay as raw material, then loaded catalyst is made using molybdenum, nickel, manganese as active component, first to C10Feedstock oil carries out hydrotreating, then hydrogenated oil obtained is placed in rectifying column, controlling tower top temperature is 130-135 DEG C, and column bottom temperature is 200-203 DEG C, carries out rectification under vacuum, gas phase in distillation process is solidifying by overhead condensation air cooling, condensate liquid flows back, and through condensing trapping device condensing trapping, the condensate liquid after trapping flows back uncooled gas phase, effectively control regurgitant volume, is made high boiling aromatic hydrocarbon solvent.This method is easy to operate, at low cost, and solvent stability obtained is good, asepsis environment-protecting.

Description

A kind of preparation method of the high boiling aromatic hydrocarbon solvent for insecticide emulsion
Technical field
The present invention relates to solvent naphtha fields, are specifically related to a kind of system of high boiling aromatic hydrocarbon solvent for insecticide emulsion Preparation Method.
Background technique
About 2,000,000 tons of China's pesticidal preparations annual output, wherein missible oil yield accounts for about 50%, using 300,000 tons of solvent or so, Mostly high volatile aromatic hydrocarbons, such as benzene,toluene,xylene.Influence for reduction organic solvent volatilization to environment, 2006 Year, former Industry Division, National Development and Reform Commission is by investigation and is expounded through peer review, and determines to be only suitable for preparing except some in due course Outside the Pesticidal products of missible oil, stop producing by the missible oil product of solvent of aromatic hydrocarbons such as benzene,toluene,xylenes.
Determine that heavy aromatics and biomass solvent, heavy aromatics are the by-product in petroleum and coal process compared with safety solvent C9 or more aromatic hydrocarbons does the aromatic hydrocarbons that mainly boiling range is 165~290 DEG C, carbon number range is C9~C16 that pesticide solvent uses.It is raw Substance solvent is that can be used for the solvent of chemical industry purposes by separation, purifying, modification, allotment, and molten using natural products as raw material It is safe to people, animal and environment that agent itself, which has relevant data proof,.Higher boiling heavy aromatic solvent oil is C+9Heavy aromatics Most bulk product, the novel dissolvent oil occurred in recent years, not aqueous, hydrocarbon, chlorine and heavy metal have excellent solvability and change Physical stability is learned, and boiling point is high, volatilization is slow, good fluidity, can be used as coating, the washing for printing ink, precision mechanical part Agent, farm chemical emulgent, amine baking varnish, amino-alkyd resin, polyurethane top grade paint, grade colour-wash diluent and paper pulp Lustering and damp-proof agent, Ink conditioning agent etc..
Summary of the invention
The object of the present invention is to provide a kind of preparation method of high boiling aromatic hydrocarbon solvent for insecticide emulsion, this method Solvent stability obtained is good, and boiling point is high, nontoxic, environmental protection, when being used for insecticide emulsion, cooperates emulsifiability with common emulsifier It is good.
To achieve the above object, the invention adopts the following technical scheme:
A kind of preparation method of the high boiling aromatic hydrocarbon solvent for insecticide emulsion, comprising the following steps:
(1) it by corn straw smashing, is then mixed with flyash, paper pulp mud, nano-titanium oxide, clay, grinding is made Mixed-powder obtained and dehydrated alcohol mixing and ball milling are handled 10-20h, filter after ball-milling treatment, solid is done by mixed-powder It is dry, it then places it in crucible, and crucible is placed in Muffle furnace, sintering processes 5-20min under air atmosphere, sintering terminates Porous carrier is made in furnace cooling afterwards；
(2) five water nitric acid molybdenums, nickel nitrate, four nitric hydrate manganese and deionized water are uniformly mixed, it is molten that mixing is made Sodium ethylene diamine tetracetate, ethylene glycol and deionized water are mixed evenly liquid A, and mixed solution B is made；
(3) after mixing mixed solution A, mixed solution B, porous carrier made from step (1) is added, is to slowly warm up to 30-50 DEG C, the sodium hydroxide solution that mass concentration is 5-8% is added dropwise, is stirred when being added dropwise, continues stirring precipitating after completion of dropwise addition 10-40min；Filtering, the precipitating of collection successively use deionized water and dehydrated alcohol to wash, loaded catalyst are made；
(4) by loaded catalyst obtained above and C10Feedstock oil is added in reactor, is passed through hydrogen, is carried out anti- It answers, removes catalyst after reaction, hydrogenated oil is made；
(5) hydrogenated oil obtained above is placed in rectifying column, control tower top temperature is 130-135 DEG C, tower bottom temperature Degree is 200-203 DEG C, carries out rectification under vacuum, and the gas phase in distillation process is solidifying by overhead condensation air cooling, and condensate liquid flows back, Through condensing trapping device condensing trapping, the condensate liquid after trapping flows back uncooled gas phase, effectively control regurgitant volume, is made high boiling Point aromatic solvent.
As a preferred embodiment of the above technical solution, in step (1), corn stover, flyash, paper pulp mud, nano-titanium oxide, The dosage of clay is respectively as follows: 15-35 parts of corn stover, 10-20 parts of flyash, 3-7 parts of paper pulp mud, nano oxygen in parts by weight Change titanium 0.1-0.6 parts, 2-5 parts of clay.
As a preferred embodiment of the above technical solution, in step (1), the temperature of the sintering processes is 800-900 DEG C.
As a preferred embodiment of the above technical solution, in step (2), in mixed solution A, the concentration of each metal ion is respectively as follows: Molybdenum ion 1-3mol/L, nickel ion 0.5-1.5mol/L, manganese ion 1-2mol/L.
As a preferred embodiment of the above technical solution, in step (2), in mixed solution B, the mass concentration of each component is respectively as follows: Sodium ethylene diamine tetracetate 2-9%, ethylene glycol 5-7%.
As a preferred embodiment of the above technical solution, in step (2), nickel nitrate, sodium ethylene diamine tetracetate mass ratio be 3: (0.5-1)。
As a preferred embodiment of the above technical solution, in step (3), porous carrier, nickel nitrate mass ratio be 6:(1-3).
As a preferred embodiment of the above technical solution, in step (4), the condition of the reaction are as follows: 120-150 DEG C, hydrogen pressure is 5- 10MPa, hydrogen-oil ratio 500-800, volume space velocity 3-10h-1。
As a preferred embodiment of the above technical solution, in step (4), the loaded catalyst, C10Amount ratio be (10-20) Mg:0.5L.
As a preferred embodiment of the above technical solution, in step (5), the fraction that when rectifying collects is 145-175 DEG C and 175- 210 DEG C of fraction.
Compared with prior art, the invention has the following advantages that
The present invention is first with C10Feedstock oil is raw material, carries out hydrotreating, finally carries out rectification process, collects 145-175 DEG C and 175-210 DEG C of fraction, high boiling aromatic hydrocarbon solvent is made；Its boiling point is high, and thermal stability is good, compatible with all kinds of emulsifiers Property is good；
The present invention uses homemade loaded catalyst in hydrogenation process, and catalytic activity is high, and dosage is few, no poison ring It protects, which is to be using corn stover, flyash, paper pulp mud, nano-titanium oxide, clay as porous ceramic grain made from raw material Carrier, using molybdenum, manganese, nickel as catalytic active component, preparation cost is low.
Specific embodiment
In order to better understand the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solving The present invention is released, any restriction will not be constituted to the present invention.
Embodiment 1
A kind of preparation method of the high boiling aromatic hydrocarbon solvent for insecticide emulsion, comprising the following steps:
(1) it by corn straw smashing, is then mixed with flyash, paper pulp mud, nano-titanium oxide, clay, grinding is made Mixed-powder obtained and dehydrated alcohol mixing and ball milling are handled 10h, filtered after ball-milling treatment by mixed-powder, and solid is dry, Then it places it in crucible, and crucible is placed in Muffle furnace, sintering processes 5min at 800-900 DEG C under air atmosphere is burnt Porous carrier is made in furnace cooling after knot；Wherein, dosage of each component is respectively as follows: 15 parts of corn stover, powder in parts by weight 10 parts of coal ash, 3 parts of paper pulp mud, 0.1 part of nano-titanium oxide, 2 parts of clay；
(2) five water nitric acid molybdenums, nickel nitrate, four nitric hydrate manganese and deionized water are uniformly mixed, it is molten that mixing is made Sodium ethylene diamine tetracetate, ethylene glycol and deionized water are mixed evenly liquid A, and mixed solution B is made；Wherein, mixed solution In A, the concentration of each metal ion is respectively as follows: molybdenum ion 1mol/L, nickel ion 0.5mol/L, manganese ion 1mol/L；Mixed solution B In, the mass concentration of each component is respectively as follows: sodium ethylene diamine tetracetate 2%, ethylene glycol 5%；Nickel nitrate, sodium ethylene diamine tetracetate Mass ratio is 3:0.5；
(3) after mixing mixed solution A, mixed solution B, porous carrier made from step (1) is added, is to slowly warm up to 30-50 DEG C, the sodium hydroxide solution that mass concentration is 5% is added dropwise, is stirred when being added dropwise, continues stirring precipitating after completion of dropwise addition 10min；Filtering, the precipitating of collection successively use deionized water and dehydrated alcohol to wash, loaded catalyst are made；Wherein, more Hole carrier, nickel nitrate mass ratio be 6:1；
(4) by loaded catalyst obtained above and C10Feedstock oil is added in reactor, is passed through hydrogen, is carried out anti- It answers, removes catalyst after reaction, hydrogenated oil is made；Wherein, the loaded catalyst, C10Amount ratio be 10mg:0.5L；
(5) hydrogenated oil obtained above is placed in rectifying column, control tower top temperature is 130-135 DEG C, tower bottom temperature Degree is 200-203 DEG C, carries out rectification under vacuum, and the gas phase in distillation process is solidifying by overhead condensation air cooling, and condensate liquid flows back, Through condensing trapping device condensing trapping, the condensate liquid after trapping flows back uncooled gas phase, effectively control regurgitant volume, is made high boiling Point aromatic solvent.
Embodiment 2
A kind of preparation method of the high boiling aromatic hydrocarbon solvent for insecticide emulsion, comprising the following steps:
(1) it by corn straw smashing, is then mixed with flyash, paper pulp mud, nano-titanium oxide, clay, grinding is made Mixed-powder obtained and dehydrated alcohol mixing and ball milling are handled 20h, filtered after ball-milling treatment by mixed-powder, and solid is dry, Then it places it in crucible, and crucible is placed in Muffle furnace, sintering processes 20min at 800-900 DEG C under air atmosphere is burnt Porous carrier is made in furnace cooling after knot；Wherein, dosage of each component is respectively as follows: 35 parts of corn stover, powder in parts by weight 20 parts of coal ash, 7 parts of paper pulp mud, 0.6 part of nano-titanium oxide, 5 parts of clay；
(2) five water nitric acid molybdenums, nickel nitrate, four nitric hydrate manganese and deionized water are uniformly mixed, it is molten that mixing is made Sodium ethylene diamine tetracetate, ethylene glycol and deionized water are mixed evenly liquid A, and mixed solution B is made；Wherein, mixed solution In A, the concentration of each metal ion is respectively as follows: molybdenum ion 3mol/L, nickel ion 1.5mol/L, manganese ion 2mol/L；Mixed solution B In, the mass concentration of each component is respectively as follows: sodium ethylene diamine tetracetate 9%, ethylene glycol 7%；Nickel nitrate, sodium ethylene diamine tetracetate Mass ratio is 3:1；
(3) after mixing mixed solution A, mixed solution B, porous carrier made from step (1) is added, is to slowly warm up to 30-50 DEG C, the sodium hydroxide solution that mass concentration is 8% is added dropwise, is stirred when being added dropwise, continues stirring precipitating after completion of dropwise addition 40min；Filtering, the precipitating of collection successively use deionized water and dehydrated alcohol to wash, loaded catalyst are made；Wherein, more Hole carrier, nickel nitrate mass ratio be 6:3；
(4) by loaded catalyst obtained above and C10Feedstock oil is added in reactor, is passed through hydrogen, is carried out anti- It answers, removes catalyst after reaction, hydrogenated oil is made；Wherein, the loaded catalyst, C10Amount ratio be 20mg:0.5L；
(5) hydrogenated oil obtained above is placed in rectifying column, control tower top temperature is 130-135 DEG C, tower bottom temperature Degree is 200-203 DEG C, carries out rectification under vacuum, and the gas phase in distillation process is solidifying by overhead condensation air cooling, and condensate liquid flows back, Through condensing trapping device condensing trapping, the condensate liquid after trapping flows back uncooled gas phase, effectively control regurgitant volume, is made high boiling Point aromatic solvent.
Embodiment 3
A kind of preparation method of the high boiling aromatic hydrocarbon solvent for insecticide emulsion, comprising the following steps:
(1) it by corn straw smashing, is then mixed with flyash, paper pulp mud, nano-titanium oxide, clay, grinding is made Mixed-powder obtained and dehydrated alcohol mixing and ball milling are handled 12h, filtered after ball-milling treatment by mixed-powder, and solid is dry, Then it places it in crucible, and crucible is placed in Muffle furnace, sintering processes 10min at 800-900 DEG C under air atmosphere is burnt Porous carrier is made in furnace cooling after knot；Wherein, dosage of each component is respectively as follows: 18 parts of corn stover, powder in parts by weight 12 parts of coal ash, 4 parts of paper pulp mud, 0.2 part of nano-titanium oxide, 3 parts of clay；
(2) five water nitric acid molybdenums, nickel nitrate, four nitric hydrate manganese and deionized water are uniformly mixed, it is molten that mixing is made Sodium ethylene diamine tetracetate, ethylene glycol and deionized water are mixed evenly liquid A, and mixed solution B is made；Wherein, mixed solution In A, the concentration of each metal ion is respectively as follows: molybdenum ion 1.5mol/L, nickel ion 0.7mol/L, manganese ion 1.2mol/L；Mixing In solution B, the mass concentration of each component is respectively as follows: sodium ethylene diamine tetracetate 3%, ethylene glycol 5.5%；Nickel nitrate, ethylenediamine tetraacetic The mass ratio of sodium acetate is 3:0.6；
(3) after mixing mixed solution A, mixed solution B, porous carrier made from step (1) is added, is to slowly warm up to 30-50 DEG C, the sodium hydroxide solution that mass concentration is 5.5% is added dropwise, is stirred when being added dropwise, continues stirring precipitating after completion of dropwise addition 20min；Filtering, the precipitating of collection successively use deionized water and dehydrated alcohol to wash, loaded catalyst are made；Wherein, more Hole carrier, nickel nitrate mass ratio be 6:1.5；
(4) by loaded catalyst obtained above and C10Feedstock oil is added in reactor, is passed through hydrogen, is carried out anti- It answers, removes catalyst after reaction, hydrogenated oil is made；Wherein, the loaded catalyst, C10Amount ratio be 12mg:0.5L；
(5) hydrogenated oil obtained above is placed in rectifying column, control tower top temperature is 130-135 DEG C, tower bottom temperature Degree is 200-203 DEG C, carries out rectification under vacuum, and the gas phase in distillation process is solidifying by overhead condensation air cooling, and condensate liquid flows back, Through condensing trapping device condensing trapping, the condensate liquid after trapping flows back uncooled gas phase, effectively control regurgitant volume, is made high boiling Point aromatic solvent.
Embodiment 4
A kind of preparation method of the high boiling aromatic hydrocarbon solvent for insecticide emulsion, comprising the following steps:
(1) it by corn straw smashing, is then mixed with flyash, paper pulp mud, nano-titanium oxide, clay, grinding is made Mixed-powder obtained and dehydrated alcohol mixing and ball milling are handled 14h, filtered after ball-milling treatment by mixed-powder, and solid is dry, Then it places it in crucible, and crucible is placed in Muffle furnace, sintering processes 10min at 800-900 DEG C under air atmosphere is burnt Porous carrier is made in furnace cooling after knot；Wherein, dosage of each component is respectively as follows: 22 parts of corn stover, powder in parts by weight 14 parts of coal ash, 4 parts of paper pulp mud, 0.3 part of nano-titanium oxide, 3 parts of clay；
(2) five water nitric acid molybdenums, nickel nitrate, four nitric hydrate manganese and deionized water are uniformly mixed, it is molten that mixing is made Sodium ethylene diamine tetracetate, ethylene glycol and deionized water are mixed evenly liquid A, and mixed solution B is made；Wherein, mixed solution In A, the concentration of each metal ion is respectively as follows: molybdenum ion 2mol/L, nickel ion 0.9mol/L, manganese ion 1.4mol/L；It mixes molten In liquid B, the mass concentration of each component is respectively as follows: sodium ethylene diamine tetracetate 5%, ethylene glycol 6%；Nickel nitrate, ethylenediamine tetra-acetic acid The mass ratio of sodium is 3:0.7；
(3) after mixing mixed solution A, mixed solution B, porous carrier made from step (1) is added, is to slowly warm up to 30-50 DEG C, the sodium hydroxide solution that mass concentration is 7% is added dropwise, is stirred when being added dropwise, continues stirring precipitating after completion of dropwise addition 30min；Filtering, the precipitating of collection successively use deionized water and dehydrated alcohol to wash, loaded catalyst are made；Wherein, more Hole carrier, nickel nitrate mass ratio be 6:2；
(4) by loaded catalyst obtained above and C10Feedstock oil is added in reactor, is passed through hydrogen, is carried out anti- It answers, removes catalyst after reaction, hydrogenated oil is made；Wherein, the loaded catalyst, C10Amount ratio be 14mg:0.5L；
(5) hydrogenated oil obtained above is placed in rectifying column, control tower top temperature is 130-135 DEG C, tower bottom temperature Degree is 200-203 DEG C, carries out rectification under vacuum, and the gas phase in distillation process is solidifying by overhead condensation air cooling, and condensate liquid flows back, Through condensing trapping device condensing trapping, the condensate liquid after trapping flows back uncooled gas phase, effectively control regurgitant volume, is made high boiling Point aromatic solvent.
Embodiment 5
A kind of preparation method of the high boiling aromatic hydrocarbon solvent for insecticide emulsion, comprising the following steps:
(1) it by corn straw smashing, is then mixed with flyash, paper pulp mud, nano-titanium oxide, clay, grinding is made Mixed-powder obtained and dehydrated alcohol mixing and ball milling are handled 16h, filtered after ball-milling treatment by mixed-powder, and solid is dry, Then it places it in crucible, and crucible is placed in Muffle furnace, sintering processes 15min at 800-900 DEG C under air atmosphere is burnt Porous carrier is made in furnace cooling after knot；Wherein, dosage of each component is respectively as follows: 26 parts of corn stover, powder in parts by weight 16 parts of coal ash, 6 parts of paper pulp mud, 0.4 part of nano-titanium oxide, 4 parts of clay；
(2) five water nitric acid molybdenums, nickel nitrate, four nitric hydrate manganese and deionized water are uniformly mixed, it is molten that mixing is made Sodium ethylene diamine tetracetate, ethylene glycol and deionized water are mixed evenly liquid A, and mixed solution B is made；Wherein, mixed solution In A, the concentration of each metal ion is respectively as follows: molybdenum ion 2.5mol/L, nickel ion 1.1mol/L, manganese ion 1.6mol/L；Mixing In solution B, the mass concentration of each component is respectively as follows: sodium ethylene diamine tetracetate 6%, ethylene glycol 6%；Nickel nitrate, ethylenediamine tetrem The mass ratio of sour sodium is 3:0.8；
(3) after mixing mixed solution A, mixed solution B, porous carrier made from step (1) is added, is to slowly warm up to 30-50 DEG C, the sodium hydroxide solution that mass concentration is 7% is added dropwise, is stirred when being added dropwise, continues stirring precipitating after completion of dropwise addition 30min；Filtering, the precipitating of collection successively use deionized water and dehydrated alcohol to wash, loaded catalyst are made；Wherein, more Hole carrier, nickel nitrate mass ratio be 6:2.5；
(4) by loaded catalyst obtained above and C10Feedstock oil is added in reactor, is passed through hydrogen, is carried out anti- It answers, removes catalyst after reaction, hydrogenated oil is made；Wherein, the loaded catalyst, C10Amount ratio be 16mg:0.5L；
(5) hydrogenated oil obtained above is placed in rectifying column, control tower top temperature is 130-135 DEG C, tower bottom temperature Degree is 200-203 DEG C, carries out rectification under vacuum, and the gas phase in distillation process is solidifying by overhead condensation air cooling, and condensate liquid flows back, Through condensing trapping device condensing trapping, the condensate liquid after trapping flows back uncooled gas phase, effectively control regurgitant volume, is made high boiling Point aromatic solvent.
Embodiment 6
A kind of preparation method of the high boiling aromatic hydrocarbon solvent for insecticide emulsion, comprising the following steps:
(1) it by corn straw smashing, is then mixed with flyash, paper pulp mud, nano-titanium oxide, clay, grinding is made Mixed-powder obtained and dehydrated alcohol mixing and ball milling are handled 10-20h, filter after ball-milling treatment, solid is done by mixed-powder It is dry, it then places it in crucible, and crucible is placed in Muffle furnace, sintering processes at 800-900 DEG C under air atmosphere Porous carrier is made in 15min, furnace cooling after sintering；Wherein, dosage of each component is respectively as follows: corn stalk in parts by weight 30 parts of stalk, 18 parts of flyash, 6.5 parts of paper pulp mud, 0.5 part of nano-titanium oxide, 4.5 parts of clay；
(2) five water nitric acid molybdenums, nickel nitrate, four nitric hydrate manganese and deionized water are uniformly mixed, it is molten that mixing is made Sodium ethylene diamine tetracetate, ethylene glycol and deionized water are mixed evenly liquid A, and mixed solution B is made；Wherein, mixed solution In A, the concentration of each metal ion is respectively as follows: molybdenum ion 2.5mol/L, nickel ion 1.4mol/L, manganese ion 1.6mol/L；Mixing In solution B, the mass concentration of each component is respectively as follows: sodium ethylene diamine tetracetate 8.5%, ethylene glycol 6.5%；Nickel nitrate, ethylenediamine The mass ratio of tetraacethyl sodium is 3:0.9；
(3) after mixing mixed solution A, mixed solution B, porous carrier made from step (1) is added, is to slowly warm up to 30-50 DEG C, the sodium hydroxide solution that mass concentration is 7.5% is added dropwise, is stirred when being added dropwise, continues stirring precipitating after completion of dropwise addition 35min；Filtering, the precipitating of collection successively use deionized water and dehydrated alcohol to wash, loaded catalyst are made；Wherein, more Hole carrier, nickel nitrate mass ratio be 6:2.5；
(4) by loaded catalyst obtained above and C10Feedstock oil is added in reactor, is passed through hydrogen, is carried out anti- It answers, removes catalyst after reaction, hydrogenated oil is made；Wherein, the loaded catalyst, C10Amount ratio be 18mg:0.5L；
(5) hydrogenated oil obtained above is placed in rectifying column, control tower top temperature is 130-135 DEG C, tower bottom temperature Degree is 200-203 DEG C, carries out rectification under vacuum, and the gas phase in distillation process is solidifying by overhead condensation air cooling, and condensate liquid flows back, Through condensing trapping device condensing trapping, the condensate liquid after trapping flows back uncooled gas phase, effectively control regurgitant volume, is made high boiling Point aromatic solvent.
1, high boiling aromatic hydrocarbon solvent property produced by the present invention is as shown in table 1:
Table 1
145-175 DEG C of fraction 175-210 DEG C of fraction
Color Transparency liquid Transparency liquid
Density (20 DEG C, kg/m3) 860-870 875-900
Total sulfur content (mg/kg) < 0.1 < 0.1
2, dissolution is mixed in raw medicine, neopelex, auxiliary agent, high boiling aromatic hydrocarbon solvent produced by the present invention To homogeneous transparent, and it is tested for the property.
Stability of emulsion test is carried out with reference to standard GB/T/T1603-2001 " pesticidal emulsion 4stability determination "； Cold storage stability test is carried out with reference to standard GB/T/T19137-2003 " pesticide low-temperature stability measuring method "；Heat storage is stablized Property test with reference to standard GB/T/Tl9136-2003 " pesticide heat storage stability measuring method " carry out；Field control effectiveness test according to Ministry of Agriculture's pesticide field efficacy medicine test criterion carries out.Test result is as follows:
Table 2
High boiling aromatic hydrocarbon solvent produced by the present invention is applied in 40% missible oil of chlopyrifos, 20 generations of indoor continuous raising Beet armyworm third-instar larvae, under room temperature, relative humidity 70 ± 5%, periodicity of illumination 14/10h (L/D) is dilute by sample with liquid-transfering gun 2000 times are interpreted into, each processing number of repetition is 3, and each target number that repeats is 50, and " pesticide indoor biometrics experiment criterion is looked in production Insecticide " in dip method test.Test result shows: the 10h death rate is 63.5-70.5%, and the 30h death rate is 83.5- 92%, the 48h death rate are 97.5% or more.

Claims (10)

1. a kind of preparation method of the high boiling aromatic hydrocarbon solvent for insecticide emulsion, which comprises the following steps:
(1) it by corn straw smashing, is then mixed with flyash, paper pulp mud, nano-titanium oxide, clay, grinds and mixing is made Mixed-powder obtained and dehydrated alcohol mixing and ball milling are handled 10-20h, filtered after ball-milling treatment by powder, and solid is dry, Then it places it in crucible, and crucible is placed in Muffle furnace, sintering processes 5-20min under air atmosphere, after sintering Porous carrier is made in furnace cooling；
(2) five water nitric acid molybdenums, nickel nitrate, four nitric hydrate manganese and deionized water are uniformly mixed, mixed solution A are made, Sodium ethylene diamine tetracetate, ethylene glycol and deionized water are mixed evenly, mixed solution B is made；
(3) after mixing mixed solution A, mixed solution B, porous carrier made from step (1) is added, is to slowly warm up to 30-50 DEG C, the sodium hydroxide solution that mass concentration is 5-8% is added dropwise, is stirred when being added dropwise, continues stirring precipitating 10- after completion of dropwise addition 40min；Filtering, the precipitating of collection successively use deionized water and dehydrated alcohol to wash, loaded catalyst are made；
(4) by loaded catalyst obtained above and C10Feedstock oil is added in reactor, is passed through hydrogen, is reacted, instead Catalyst is removed after answering, and hydrogenated oil is made；
(5) hydrogenated oil obtained above is placed in rectifying column, control tower top temperature is 130-135 DEG C, and column bottom temperature is 200-203 DEG C, rectification under vacuum is carried out, the gas phase in distillation process is solidifying by overhead condensation air cooling, and condensate liquid flows back, not cold Gas phase is coagulated through condensing trapping device condensing trapping, and the condensate liquid after trapping flows back, effectively control regurgitant volume, and higher boiling virtue is made Hydrocarbon solvent.
2. a kind of preparation method of the high boiling aromatic hydrocarbon solvent for insecticide emulsion as described in claim 1, feature exist In, in step (1), corn stover, flyash, paper pulp mud, nano-titanium oxide, clay dosage be respectively as follows: in parts by weight 15-35 parts of corn stover, 10-20 parts of flyash, 3-7 parts of paper pulp mud, 0.1-0.6 parts of nano-titanium oxide, 2-5 parts of clay.
3. a kind of preparation method of the high boiling aromatic hydrocarbon solvent for insecticide emulsion as described in claim 1, feature exist In in step (1), the temperature of the sintering processes is 800-900 DEG C.
4. a kind of preparation method of the high boiling aromatic hydrocarbon solvent for insecticide emulsion as described in claim 1, feature exist In in step (2), in mixed solution A, the concentration of each metal ion is respectively as follows: molybdenum ion 1-3mol/L, nickel ion 0.5- 1.5mol/L, manganese ion 1-2mol/L.
5. a kind of preparation method of the high boiling aromatic hydrocarbon solvent for insecticide emulsion as described in claim 1, feature exist In in step (2), in mixed solution B, the mass concentration of each component is respectively as follows: sodium ethylene diamine tetracetate 2-9%, ethylene glycol 5- 7%。
6. a kind of preparation method of the high boiling aromatic hydrocarbon solvent for insecticide emulsion as described in claim 1, feature exist In, in step (2), nickel nitrate, sodium ethylene diamine tetracetate mass ratio be 3:(0.5-1).
7. a kind of preparation method of the high boiling aromatic hydrocarbon solvent for insecticide emulsion as described in claim 1, feature exist In, in step (3), porous carrier, nickel nitrate mass ratio be 6:(1-3).
8. a kind of preparation method of the high boiling aromatic hydrocarbon solvent for insecticide emulsion as described in claim 1, feature exist In, in step (4), the condition of the reaction are as follows: 120-150 DEG C, hydrogen pressure is 5-10MPa, hydrogen-oil ratio 500-800, volume sky Speed is 3-10h-1。
9. a kind of preparation method of the high boiling aromatic hydrocarbon solvent for insecticide emulsion as described in claim 1, feature exist In, in step (4), the loaded catalyst, C10Amount ratio be (10-20) mg:0.5L.
10. a kind of preparation method of the high boiling aromatic hydrocarbon solvent for insecticide emulsion as described in claim 1, feature exist In, in step (5), fraction that the fraction that when rectifying collects is 145-175 DEG C and 175-210 DEG C.
CN201811382709.7A 2018-11-20 2018-11-20 A kind of preparation method of the high boiling aromatic hydrocarbon solvent for insecticide emulsion Pending CN109456796A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104152179A (en) * 2014-09-01 2014-11-19 江苏联东化工股份有限公司 Production method of high-boiling-point aromatic solvent oil
CN105132019A (en) * 2015-09-28 2015-12-09 吴江市万事达环保溶剂有限公司 Preparation method for high-boiling-point aromatic solvent oil

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104152179A (en) * 2014-09-01 2014-11-19 江苏联东化工股份有限公司 Production method of high-boiling-point aromatic solvent oil
CN105132019A (en) * 2015-09-28 2015-12-09 吴江市万事达环保溶剂有限公司 Preparation method for high-boiling-point aromatic solvent oil

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