CN108949266B - Viscosity-reducing polymerization inhibitor for wood tar and preparation method and application thereof - Google Patents
Viscosity-reducing polymerization inhibitor for wood tar and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
- C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
- C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
- C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
Abstract
The invention belongs to the technical field of fuel oil additives, and particularly relates to a wood tar viscosity-reducing polymerization inhibitor, and a preparation method and application thereof. The viscosity-reducing polymerization inhibitor comprises the following components in parts by weight: 43-49 parts of alcohol compound, 1-2 parts of phenolic compound, 0.5-4 parts of amine compound and 0.2-0.6 part of surfactant. According to the viscosity-reducing polymerization inhibitor for wood tar, alcohol compounds mainly play a role in diluting and reducing viscosity, and on the other hand, hydroxyl groups in the alcohol compounds are combined with aldehyde groups or carboxyl groups in the wood tar, so that the occurrence of condensation polycondensation reaction in a system is reduced; the amine compound can slow down the condensation polymerization speed of the aldehyde ketone substances of the wood tar under the acidic or alkaline condition by adjusting the acid value of the wood tar; in addition, the amine compound and the added phenolic compound play a synergistic polymerization inhibition effect, and have an obvious polymerization inhibition effect on the polymerization of furfural substances in the wood tar.
Description
Technical Field
The invention belongs to the technical field of fuel oil additives, and particularly relates to a wood tar viscosity-reducing polymerization inhibitor, and a preparation method and application thereof.
Background
The wood tar is a dark brown liquid obtained by condensing and liquefying condensable gas in the biomass pyrolysis liquefaction process, has sharp smoke smell, and can generate various polycondensation reactions in the storage process due to the fact that the wood tar contains a large amount of complex substances such as small molecular organic acids, aldehydes and ketones, esters, phenol derivatives, lignin oligomers and the like, so that the viscosity of the wood tar is slowly increased in the storage process, and the wood tar is layered in the storage process due to moisture generated by polycondensation; under the condition of heating, the polycondensation speed is accelerated, the viscosity of the wood tar is rapidly increased, and the sticky substances can form coke at a higher temperature, so that the wood tar has the defects of high viscosity and high heat sensitivity, the problems of rapid catalyst inactivation, coking and blockage of pipelines and the like exist in the subsequent processing process of the wood tar, and the subsequent processing process of the wood tar, such as the processes of hydrogenation upgrading, catalytic esterification, catalytic cracking and the like of the wood tar, is very unfavorable.
At present, few domestic reports on wood tar viscosity reduction and polymerization inhibition exist, and no related patent report is found. In the prior art, Chinese patent CN10197947A discloses a special coke inhibitor for hydrogenation of coal tar and crude benzene, which is characterized in that: the hydrogen-supplying and coking-resisting agent is formed by mixing a polymerization-resisting and coking-resisting component and a hydrogen-supplying and stabilizing component, wherein the weight percentage of the two components is 45-55% and 55-45% respectively; the polymerization-resistant and anti-coking component is a mixture consisting of an organic phosphorus compound, a phenol compound, an amine compound, a high molecular weight polyamine and an organic sulfide, and the weight percentage contents are respectively as follows: 5-10%, 10-30%, 30-40% and 5-10%. Wherein, the phenolic compound has better free oxygen resistance and coking inhibition effects; the amine compound has the capability of blocking free radical chain reaction, can form inert molecules with active free radicals, stops the free radical chain reaction and prevents and reduces the generation of macromolecular organic polymers; the high molecular weight amine compound has solubilization and dispersibility, can perform solubilization on a macromolecular polymer formed in the raw material to prevent the macromolecular polymer from being separated out from a material flow, has a dispersion effect on small coke particles in the raw material to prevent the small coke particles from being aggregated and deposited on the surface of equipment; the organic sulfur compound can inhibit the promotion effect of nickel in the furnace tube material on the coking, thereby inhibiting the coking. The mixtures obtained by the substances in different proportions can play roles in inhibiting polymerization, dispersing, dissolving scales and the like in the hydrogenation process of coal tar and crude benzene. However, in the wood tar system, because the system is rich in a large amount of carboxylic acid, aldehyde ketone and phenolic compounds, intermolecular acetalization reaction and hemiacetalization reaction occur between the aldehyde compounds and alcohols under the condition of heating or in the presence of acid as a catalyst; reacting phenol and formaldehyde to generate o-hydroxymethyl phenol or a phenolic compound; aldehydes and phenols undergo dehydration condensation reaction to produce phenolic resins and the like, most of the polymers are polycondensation products, the polymerization inhibition mechanism of the polymers is different from that of special coke inhibitors for hydrogenation of coal tar and crude benzene disclosed in the CN10197947A patent, and the polymerization inhibition and coke inhibition agent in the CN10197947A patent mainly aims at free radical polymerization, so that the polymerization inhibition and coke inhibition agent in the CN10197947A patent is not suitable for a wood tar system.
Disclosure of Invention
Therefore, the invention aims to overcome the defects of high low-temperature viscosity, easy polycondensation at high temperature, coking and the like of wood tar in the prior art, thereby providing the wood tar viscosity-reducing polymerization inhibitor.
In order to solve the technical problems, the invention adopts the following technical scheme:
the viscosity-reducing polymerization inhibitor for wood tar comprises the following components in parts by weight: 43-49 parts of alcohol compound, 1-2 parts of phenolic compound, 0.5-4 parts of amine compound and 0.2-0.6 part of surfactant.
Preferably, the composition comprises the following components in parts by weight: 45-47 parts of alcohol compounds, 1-2 parts of phenolic compounds, 2-3 parts of amine compounds and 0.2-0.5 part of surfactant.
Further, the alcohol compound is selected from one or more of methanol, ethanol, isopropanol, isobutanol or isooctanol.
Further, the phenolic compound is selected from one or more of hydroquinone, p-benzoquinone, p-tert-butyl catechol, methyl hydroquinone or 2, 6-di-tert-butyl-p-cresol.
Further, the amine compound is selected from one or more of diphenylamine, N-phenyl-2-naphthylamine or 2,2, 4-trimethyl-1, 2-dihydroquinoline.
Further, the surfactant is an oil-in-water emulsifier.
Further, the surfactant is selected from one or more of polyethylene glycol, sodium dodecyl sulfate or tween.
The preparation method of the wood tar viscosity-reducing polymerization inhibitor comprises the following steps: weighing the components in proportion, mixing the phenolic compound, the amine compound and the surfactant, and dissolving the mixture in the alcohol compound.
The application of the wood tar viscosity-reducing polymerization inhibitor is characterized in that the addition amount of the wood tar viscosity-reducing polymerization inhibitor is 1-50 wt%.
Preferably, the addition amount of the wood tar viscosity-reducing polymerization inhibitor is 4-10 wt%.
The technical scheme of the invention has the following advantages:
1. the viscosity-reducing polymerization inhibitor for wood tar provided by the invention comprises the following components in parts by weight: 43-49 parts of alcohol compound, 1-2 parts of phenolic compound, 0.5-4 parts of amine compound and 0.2-0.6 part of surfactant. The multifunctional viscosity-reducing polymerization inhibitor is formed by compounding an alcohol compound, phenols and an amine compound, so that the problems of thermal stability and stability of the wood tar in the storage and processing process are solved.
According to the viscosity-reducing polymerization inhibitor for wood tar, alcohol compounds mainly play a role in diluting and reducing viscosity, and on the other hand, hydroxyl groups in the alcohol compounds are combined with aldehyde groups or carboxyl groups in the wood tar, so that the occurrence of condensation polycondensation reaction in a system is reduced; the amine compound can slow down the condensation polymerization speed of the aldehyde ketone substances of the wood tar under the acidic or alkaline condition by adjusting the acid value of the wood tar; in addition, the amine compound and the added phenolic compound play a synergistic polymerization inhibition effect, and have an obvious polymerization inhibition effect on the polymerization of aldehyde ketone substances in the wood tar.
Finally, the wood tar viscosity-reducing polymerization inhibitor provided by the invention is simple in components, wide in raw material source, small in toxic and side effects and low in cost.
2. The wood tar viscosity-reducing polymerization inhibitor is applied, and the addition amount of the wood tar viscosity-reducing polymerization inhibitor is 1-50 wt%. Preferably, the addition amount of the wood tar viscosity-reducing polymerization inhibitor is 5-10 wt%. Convenient to use, easy operation. At normal temperature, 10 percent of the viscosity-reducing polymerization inhibitor for wood tar is added, and the viscosity-reducing rate of the wood tar reaches 84 percent; aging for 0.5 hour at high temperature, adding 4% of the viscosity-reducing polymerization inhibitor for wood tar, the viscosity-reducing rate of the wood tar reaches 76%, the number-average molecular weight is reduced by 49% (based on the data of case 6), and the viscosity-reducing polymerization-inhibiting effect is obvious.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
The embodiment provides a wood tar viscosity-reducing polymerization inhibitor, and the specific preparation method comprises the following steps: and (2) adding 2g of p-tert-butylcatechol, 4g of diphenylamine and 0.5g of sodium dodecyl sulfate into 43g of ethanol, and uniformly mixing to prepare the wood tar viscosity-reducing polymerization inhibitor. Adding 98g of wood tar into 2g of the viscosity-reducing polymerization inhibitor, uniformly mixing, dividing into two parts, putting one part into a crystallization kettle, sealing, putting into an oven at 180 ℃, keeping the temperature for 1 hour, cooling to room temperature, measuring the viscosity of the wood tar at 20 ℃ to be 560mPa.s, and obtaining the viscosity-reducing rate of 72 percent compared with the viscosity of the wood tar aged at 180 ℃ for 1 hour (2000 mPa.s at 20 ℃) without any polymerization inhibitor. The other portion was left at room temperature for 1 month, and the viscosity of the wood tar at 20 ℃ was measured to be 246mpa.s, which was 47% lower than the viscosity of the wood tar aged at room temperature for 1 month without any polymerization inhibitor (460 mpa.s at 20 ℃).
Example 2
The embodiment provides a wood tar viscosity-reducing polymerization inhibitor, and the specific preparation method comprises the following steps: adding 45.8g of methanol into 2g of p-tert-butylcatechol, 2g N-phenyl-2-naphthylamine and 0.2g of polyethylene glycol-600, and uniformly mixing to prepare the viscosity-reducing polymerization inhibitor. And (2) adding 95g of wood tar into 5g of the viscosity-reducing polymerization inhibitor solution, uniformly mixing, dividing into two parts, putting one part into a crystallization kettle, sealing, putting into a 180 ℃ oven, keeping the temperature for 1 hour, cooling to room temperature, measuring the viscosity of the wood tar at 20 ℃ to be 460mPa.s, and measuring the viscosity of the wood tar at 180 ℃ for 1 hour (2000 mPa.s) compared with the viscosity of the wood tar aged at 180 ℃ for 1 hour without any polymerization inhibitor (the viscosity of the wood tar at 20 ℃ is measured to be 77%. The other portion was left at room temperature for 1 month, and the viscosity of the wood tar at 20 ℃ was measured to be 156mpa.s, which was 66% lower than the viscosity of the wood tar aged at room temperature for 1 month without any polymerization inhibitor (460 mpa.s at 20 ℃).
Example 3
The embodiment provides a wood tar viscosity-reducing polymerization inhibitor, and the specific preparation method comprises the following steps: taking 46.5g of ethanol, adding 2g of methyl hydroquinone, 1.5g of 2,2, 4-trimethyl-1, 2-dihydroquinoline and 0.4g of Tween 80 into the ethanol, and uniformly mixing to prepare the viscosity-reducing polymerization inhibitor. And (2) adding 98g of wood tar into 2g of the viscosity-reducing polymerization inhibitor, uniformly mixing, dividing into two parts, putting one part into a crystallization kettle, sealing, putting into a 180 ℃ oven, keeping the temperature for 1 hour, cooling to room temperature, measuring the viscosity of the wood tar at 20 ℃ to be 600mPa.s, and measuring the viscosity of the wood tar at 180 ℃ for 1 hour (2000 mPa.s) compared with the viscosity of the wood tar aged at 180 ℃ for 1 hour without any polymerization inhibitor (the viscosity of the wood tar at 20 ℃ is measured to be 70%. The other portion was left at room temperature for 1 month, and the viscosity of the wood tar at 20 ℃ was measured to be 320mpa.s, which was 30% lower than the viscosity of the wood tar aged at room temperature for 1 month without any polymerization inhibitor (460 mpa.s at 20 ℃).
Example 4
The embodiment provides a wood tar viscosity-reducing polymerization inhibitor, and the specific preparation method comprises the following steps: adding 48g of methanol into 1g of p-tert-butylcatechol, 0.8g of 0.8g N-phenyl-2-naphthylamine and 0.2g of tween-80, and uniformly mixing to prepare the viscosity-reducing polymerization inhibitor. Adding 92g of wood tar into 8g of the viscosity-reducing polymerization inhibitor solution, uniformly mixing, dividing into two parts, putting one part into a crystallization kettle, sealing, putting into a 180 ℃ oven, keeping the temperature for 0.5 hour, cooling to room temperature, measuring the viscosity of the wood tar at 20 ℃ to be 96mPa.s, and measuring the viscosity of the wood tar at 180 ℃ for 0.5 hour (760 mPa.s at 20 ℃) compared with the viscosity of the wood tar aged at 180 ℃ for 0.5 hour without adding any polymerization inhibitor, wherein the viscosity reduction rate is 87%. The other portion was left at room temperature for 1 month, and the viscosity of the wood tar at 20 ℃ was measured to be 73mpa.s, which was 84% lower than the viscosity of the wood tar aged at room temperature for 1 month without any polymerization inhibitor (460 mpa.s at 20 ℃).
Example 5
The embodiment provides a wood tar viscosity-reducing polymerization inhibitor, and the specific preparation method comprises the following steps: taking 47.4g of methanol, adding 1g of p-tert-butylcatechol, 1g of 2,2, 4-trimethyl-1, 2-dihydroquinoline and 0.6g of polyethylene glycol-600, and uniformly mixing to prepare the viscosity-reducing polymerization inhibitor. Adding 94g of wood tar into 6g of the viscosity-reducing polymerization inhibitor, uniformly mixing, dividing into two parts, putting one part into a crystallization kettle, sealing, putting into an oven at 180 ℃, keeping the temperature for 0.5 hour, cooling to room temperature, measuring the viscosity of the wood tar at 20 ℃ to be 127mPa.s, and measuring the viscosity of the wood tar at 180 ℃ for 0.5 hour (760 mPa.s at 20 ℃) compared with the viscosity of the wood tar which is aged at 180 ℃ for 0.5 hour without any polymerization inhibitor, wherein the viscosity-reducing rate is 83 percent. The other portion was left at room temperature for 1 month, and the viscosity of the wood tar at 20 ℃ was measured to be 83mpa.s, which was 82% lower than the viscosity of the wood tar aged at room temperature for 1 month without any polymerization inhibitor (460 mpa.s at 20 ℃).
Example 6
The embodiment provides a wood tar viscosity-reducing polymerization inhibitor, and the specific preparation method comprises the following steps: 49g of methanol is taken, 1.5g of p-tert-butylcatechol, 4g of 2,2, 4-trimethyl-1, 2-dihydroquinoline and 0.4g of polyethylene glycol-600 are added into the methanol, and the mixture is uniformly mixed to prepare the viscosity-reducing polymerization inhibitor. Adding 96g of wood tar into 4g of the viscosity-reducing polymerization inhibitor, uniformly mixing, dividing into two parts, putting one part into a crystallization kettle, sealing, putting into an oven at 180 ℃, keeping the temperature for 0.5 hour, cooling to room temperature, measuring the viscosity of the wood tar at 20 ℃ to be 184mPa.s, and measuring the viscosity of the wood tar at 180 ℃ for 0.5 hour (760 mPa.s at 20 ℃) compared with the viscosity of the wood tar which is aged at 180 ℃ for 0.5 hour without any polymerization inhibitor, wherein the viscosity-reducing rate is 76%. The other portion was left at room temperature for 1 month, and the viscosity of the wood tar at 20 ℃ was measured to be 150mpa.s, which was 67% lower than the viscosity of the wood tar aged at room temperature for 1 month without any polymerization inhibitor (460 mpa.s at 20 ℃).
Example 7
The embodiment provides a wood tar viscosity-reducing polymerization inhibitor, and the specific preparation method comprises the following steps: 44g of isopropanol is taken, 1.8g of hydroquinone, 3g of 2,2, 4-trimethyl-1, 2-dihydroquinoline and 0.4g of polyethylene glycol-600 are added into the isopropanol and mixed evenly to prepare the viscosity-reducing polymerization inhibitor. Adding 96g of wood tar into 4g of the viscosity-reducing polymerization inhibitor, uniformly mixing, dividing into two parts, putting one part into a crystallization kettle, sealing, putting into an oven at 180 ℃, keeping the temperature for 0.5 hour, cooling to room temperature, measuring the viscosity of the wood tar at 20 ℃ to be 315mPa.s, and measuring the viscosity of the wood tar at 180 ℃ for 0.5 hour (760 mPa.s at 20 ℃) compared with the viscosity of the wood tar which is aged at 180 ℃ for 0.5 hour without any polymerization inhibitor, wherein the viscosity-reducing rate is 59%. The other portion was left at room temperature for 1 month, and the viscosity of the wood tar at 20 ℃ was measured to be 230mpa.s, which was 50% lower than the viscosity of the wood tar aged at room temperature for 1 month without any polymerization inhibitor (460 mpa.s at 20 ℃).
Example 8
The embodiment provides a wood tar viscosity-reducing polymerization inhibitor, and the specific preparation method comprises the following steps: 46g of isooctanol is taken, 1.6g of p-benzoquinone, 2g of diphenylamine and 0.4g of sodium dodecyl sulfate are added into the isooctanol, and the mixture is uniformly mixed to prepare the viscosity-reducing polymerization inhibitor. Adding 96g of wood tar into 4g of the viscosity-reducing polymerization inhibitor, uniformly mixing, dividing into two parts, putting one part into a crystallization kettle, sealing, putting into an oven at 180 ℃, keeping the temperature for 0.5 hour, cooling to room temperature, measuring the viscosity of the wood tar at 20 ℃ to be 360mPa.s, and measuring the viscosity of the wood tar at 53 percent compared with the viscosity of the wood tar aged at 180 ℃ for 0.5 hour without any polymerization inhibitor (760 mPa.s at 20 ℃). The other portion was left at room temperature for 1 month, and the viscosity of the wood tar at 20 ℃ was determined to be 295mpa.s, which was 36% lower than the viscosity of the wood tar aged at room temperature for 1 month without any polymerization inhibitor (460 mpa.s at 20 ℃).
Comparative example 1 (No alcohol)
The comparative example provides a wood tar viscosity-reducing polymerization inhibitor, and the specific preparation method comprises the following steps: 3g of p-tert-butylcatechol, 3g of 2,2, 4-trimethyl-1, 2-dihydroquinoline and 1.8g of polyethylene glycol-600 are mixed uniformly to prepare the viscosity-reducing polymerization inhibitor. And (3) adding 94g of wood tar into 6g of the viscosity-reducing polymerization inhibitor, uniformly mixing, wherein the viscosity-reducing polymerization inhibitor is insoluble, and the viscosity of the wood tar is not measured.
COMPARATIVE EXAMPLE 2 (No phenol)
The comparative example provides a wood tar viscosity-reducing polymerization inhibitor, and the specific preparation method comprises the following steps: 47.4g of methanol is taken, 1g of 2,2, 4-trimethyl-1, 2-dihydroquinoline and 0.6g of polyethylene glycol-600 are added into the methanol, and the mixture is uniformly mixed to prepare the viscosity-reducing polymerization inhibitor. Adding 94g of wood tar into 6g of the viscosity-reducing polymerization inhibitor, uniformly mixing, dividing into two parts, putting one part into a crystallization kettle, sealing, putting into an oven at 180 ℃, keeping the temperature for 0.5 hour, cooling to room temperature, measuring the viscosity of the wood tar at 20 ℃ to be 233mPa.s, and measuring the viscosity of the wood tar at 69 percent by comparing with the viscosity of the wood tar aged at 180 ℃ for 1 hour without any polymerization inhibitor (760 mPa.s at 20 ℃). The other portion was left at room temperature for 1 month, and the viscosity of the wood tar at 20 ℃ was determined to be 229mpa.s, which is 50% lower than the viscosity of the wood tar aged at room temperature for 1 month without any polymerization inhibitor (460 mpa.s at 20 ℃).
Comparative example 3 (without amine)
The comparative example provides a wood tar viscosity-reducing polymerization inhibitor, and the specific preparation method comprises the following steps: 47.4g of methanol is taken, 1g of p-tert-butylcatechol and 0.6g of polyethylene glycol-600 are added into the methanol, and the mixture is uniformly mixed to prepare the viscosity-reducing polymerization inhibitor. Adding 94g of wood tar into 6g of the viscosity-reducing polymerization inhibitor, uniformly mixing, dividing into two parts, putting one part into a crystallization kettle, sealing, putting into an oven at 180 ℃, keeping the temperature for 0.5 hour, cooling to room temperature, measuring the viscosity of the wood tar at 20 ℃ to be 256mPa.s, and measuring the viscosity of the wood tar at 180 ℃ for 1 hour (760 mPa.s at 20 ℃) compared with the viscosity of the wood tar which is aged at 180 ℃ for 1 hour without any polymerization inhibitor, wherein the viscosity-reducing rate is 66%. The other portion was left at room temperature for 1 month, and the viscosity of the wood tar at 20 ℃ was measured to be 170mpa.s, which was 63% lower than the viscosity of the wood tar aged at room temperature for 1 month without any polymerization inhibitor (460 mpa.s at 20 ℃).
Comparative example 4 (without surfactant)
The embodiment provides a wood tar viscosity-reducing polymerization inhibitor, and the specific preparation method comprises the following steps: 47.4g of methanol is taken, 1g of p-tert-butylcatechol and 1g of 2,2, 4-trimethyl-1, 2-dihydroquinoline are added into the methanol, and the mixture is uniformly mixed to prepare the viscosity-reducing polymerization inhibitor. Adding 94g of wood tar into 6g of the viscosity-reducing polymerization inhibitor, uniformly mixing, dividing into two parts, putting one part into a crystallization kettle, sealing, putting into an oven at 180 ℃, keeping the temperature for 0.5 hour, cooling to room temperature, measuring the viscosity of the wood tar at 20 ℃ of 295mPa.s, and measuring the viscosity of the wood tar at 61 percent compared with the viscosity of the wood tar aged at 180 ℃ for 1 hour without any polymerization inhibitor (760 mPa.s at 20 ℃). The other portion was left at room temperature for 1 month, and the viscosity of the wood tar at 20 ℃ was measured to be 185mpa.s, which was 60% lower than the viscosity of the wood tar aged at room temperature for 1 month without any polymerization inhibitor (460 mpa.s at 20 ℃).
Examples of the experiments
Test method
1. In the above examples and comparative examples, the viscosity of the wood tar was measured by using a rotational viscometer of the type HADV-111+ PRO manufactured by BROOKFIELD, USA.
2. The molecular weight of the wood tar is measured by a U.S. model 833 VPO tester, and the specific test method comprises the following steps: adding a corresponding amount of the viscosity-reducing polymerization inhibitor of examples 1, 4, 6-8 and comparative examples 2-4 into wood tar, uniformly mixing, placing into a crystallization kettle, sealing, placing into an oven at 180 ℃, keeping the temperature for 0.5 hour, cooling to room temperature, and measuring the number average molecular weight of the wood tar; a sample with a certain mass is dissolved in a certain amount of acetone to prepare a series of acetone solutions of 1.29g/L, 2.58g/L, 5.16g/L and 10.33g/L, a drop of the sample solution and a drop of the solvent are respectively dropped on two thermistors of a closed chamber saturated by the solvent, gas-phase solvent molecules can be condensed on the sample solution drops due to the fact that the saturated vapor pressure of the sample solution is lower than that of the solvent, condensation heat is released, and temperature difference is generated between the two drops. Measuring the temperature change expressed as voltage output, plotting Δ V/C-C, and calculating the intercept B of the straight line1(ii) a A solution of sucrose cellulose (molecular weight 678.6) with a known molecular weight as a standard was prepared as described above, and the intercept B of the curve from Δ V/C to C was determined2And calculating a correction factor K-678.6B2When the number average molecular weight M of the sample is equal to K/B1。
TABLE 1 Effect of viscosity reducing inhibitors on Wood Coke viscosity (mPa.s)
As can be seen from the data in the table, the polymerization inhibiting and viscosity reducing effects are better as the amount of the polymerization inhibitor added is larger, and the polymerization inhibiting effect is the best in example 5. Comparing the data of comparative examples 2-4 with the data of example 5, it can be seen that the components of the viscosity-reducing polymerization inhibitor provided by the invention are synergistic and matched with each other, but none of the components is sufficient.
The effects on the molecular weight of the wood tar of examples 1, 4, 6 to 8 and comparative examples 2 to 4 of the present invention were tested, and the specific test results are shown in table 2:
TABLE 2 Effect of viscosity reducing polymerization inhibitors on the molecular weight of Wood Tar
| Adding amount of | 2％ | 4％ | 8％ | 10％ | 25％ | 50％ |
| Example 1 | 676 | 334 | 284 | 261 | 187 | 105 |
| Example 4 | 539 | 318 | 217 | 196 | 123 | 72 |
| Example 6 | 518 | 313 | 207 | 186 | 103 | 68 |
| Example 7 | 821 | 642 | 331 | 294 | 254 | 185 |
| Example 8 | 922 | 531 | 392 | 372 | 340 | 262 |
| Comparative example 2 | 756 | 418 | 330 | 290 | 236 | 154 |
| Comparative example 3 | 781 | 448 | 356 | 314 | 286 | 196 |
| Comparative example 4 | 857 | 541 | 439 | 392 | 305 | 213 |
As can be seen from the data in the table, with the increase of the addition amount of the polymerization inhibitor and viscosity reducer, the intermolecular polymerization in the system can be effectively inhibited, wherein the polymerization inhibiting effect is most obvious in the examples 4 and 6.
TABLE 3 influence of viscosity-reducing inhibitors on the molecular weight of wood tar at Normal temperature
| Adding amount of | 2％ | 4％ | 8％ | 10％ | 25％ | 50％ |
| Example 1 | 354 | 319 | 257 | 235 | 146 | 90 |
| Example 4 | 326 | 280 | 211 | 189 | 106 | 62 |
| Example 6 | 323 | 276 | 207 | 185 | 103 | 59 |
| Example 7 | 357 | 330 | 274 | 254 | 165 | 104 |
| Example 8 | 382 | 374 | 341 | 329 | 262 | 196 |
| Comparative example 2 | 403 | 371 | 298 | 241 | 176 | 102 |
| Comparative example 3 | 415 | 385 | 304 | 253 | 212 | 128 |
| Comparative example 4 | 428 | 393 | 318 | 285 | 220 | 136 |
As is clear from the data in Table 3, the polymerization inhibitor has a remarkable effect of inhibiting polymerization under high temperature conditions, and the viscosity and the number average molecular weight are greatly reduced.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (7)
1. The viscosity-reducing polymerization inhibitor for wood tar is characterized by comprising the following components in parts by weight: 43-49 parts of alcohol compound, 1-2 parts of phenolic compound, 0.5-4 parts of amine compound and 0.2-0.6 part of surfactant;
the alcohol compound is selected from one or more of methanol, ethanol, isopropanol, isobutanol or isooctanol;
the phenolic compound is selected from one or more of hydroquinone, p-benzoquinone, p-tert-butyl catechol, methyl hydroquinone or 2, 6-di-tert-butyl-p-cresol;
the amine compound is selected from one or more of diphenylamine, N-phenyl-2-naphthylamine or 2,2, 4-trimethyl-1, 2-dihydroquinoline.
2. The wood tar viscosity-reducing polymerization inhibitor according to claim 1, which comprises the following components in parts by weight: 45-47 parts of alcohol compounds, 1-2 parts of phenolic compounds, 2-3 parts of amine compounds and 0.2-0.5 part of surfactant.
3. The wood tar viscosity-reducing polymerization inhibitor according to claim 1 or 2, wherein the surfactant is an oil-in-water emulsifier.
4. The wood tar viscosity-reducing polymerization inhibitor according to claim 3, wherein the surfactant is one or more selected from polyethylene glycol, sodium dodecyl sulfate and Tween.
5. A preparation method of the viscosity-reducing polymerization inhibitor for wood tar according to any one of claims 1 to 4, which is characterized in that the components are weighed in proportion, and the phenolic compound, the amine compound and the surfactant are mixed and dissolved in the alcohol compound.
6. The use of the wood tar viscosity-reducing polymerization inhibitor according to any one of claims 1 to 4, wherein the wood tar viscosity-reducing polymerization inhibitor is added in an amount of 1 to 50 wt%.
7. The use of the wood tar viscosity-reducing polymerization inhibitor according to claim 6, wherein the wood tar viscosity-reducing polymerization inhibitor is added in an amount of 4-10 wt%.
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