CN113388417B - Heat-conducting oil online alkaline protective agent and preparation method and application thereof - Google Patents

Heat-conducting oil online alkaline protective agent and preparation method and application thereof Download PDF

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Publication number
CN113388417B
CN113388417B CN202010173383.8A CN202010173383A CN113388417B CN 113388417 B CN113388417 B CN 113388417B CN 202010173383 A CN202010173383 A CN 202010173383A CN 113388417 B CN113388417 B CN 113388417B
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China
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protective agent
heat transfer
alkaline
oil
transfer oil
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CN113388417A (en
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张觅
袁浩然
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry 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
    • C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
    • C10G19/073—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with solid alkaline material
    • 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

Abstract

The invention belongs to the technical field of protective agents, and relates to a heat conduction oil online alkaline protective agent, a preparation method and application thereof, which are used for online control of acidity and sulfur content of heat conduction oil. The protective agent consists of a solid alkaline material, a desulfurization material and a framework material. The protective agent has the functions of controlling the acidity and the sulfur content in the heat transfer oil on line, delaying the aging of the heat transfer oil and prolonging the service life of the heat transfer oil, wherein the mass percentage of the solid alkaline material is 40-70%, the mass percentage of the desulfurization material is 20-50%, and the mass percentage of the framework material is 5-10%.

Description

Heat-conducting oil online alkaline protective agent and preparation method and application thereof
Technical Field
The invention belongs to the technical field of protective agents, and particularly relates to an alkaline protective agent for the acidity and sulfur content of heat conduction oil.
Background
The acid value of the thermal oil, also called the neutralization value, refers to the total content of organic acids in the thermal oil. The acid value is expressed as the amount (mg) of potassium hydroxide required for the free acid contained in 1g of the heat transfer oil, in mgKOH/g.
When the temperature of the heat conducting oil is not more than 100 ℃ and no moisture exists, the organic acid of the heat conducting oil does not corrode metal, and when the temperature exceeds 100 ℃, the corrosivity of the organic acid to the metal is increased along with the increase of the temperature and the acid value. The acid value index is not more than 0.2, the higher the acid value is, the more acidic substances are in the heat conduction oil, which is one of the quality indexes for judging whether the aging and oxidation degree of the oil product corrodes the equipment. When organic acids react with metals to form metal salts or soaps, these materials can accelerate the aging and deterioration of oils and reduce their anti-emulsifying ability.
In addition, the increase in the value of the diathermic oil causes the diathermic oil to darken in color and release odor. In addition, soap precipitates and other oxides are easy to block pipelines and valves, so that the measurement of the acid value of the heat transfer oil in the operation process and the control of the acid value are greatly helpful for ensuring the normal operation of a heating system and heat utilization equipment. In general, heat transfer oil having an acid value exceeding 0.5mgKOH/g should be replaced. Similarly, sulfur in heat transfer oils can cause corrosion of equipment, and therefore, it is generally desirable that the sulfur content in heat transfer oils be no more than 0.2%
CN 106179375A mentions a catalyst for regenerating heat transfer oil, and uses solid alkali to protect the catalyst, and can further reduce the residual acid value in the heat transfer oil. The catalyst is applied to the disassembled waste heat conduction oil, and the regenerated heat conduction oil is obtained by pretreating the waste heat conduction oil and then hydrogenating by using the catalyst under a certain working condition. The catalyst can not be directly applied to a heat conduction oil circulating device due to the need of a hydrogen working condition.
At present, the online protective agent for heat conduction oil is rarely reported.
Disclosure of Invention
The invention aims to provide an alkaline protective agent for controlling the acidity and the sulfur content of heat transfer oil on line.
The invention also provides a preparation method and application of the heat conduction oil online alkaline protective agent.
The main technical scheme of the invention is as follows: the heat-conducting oil online alkaline protective agent is characterized by comprising a solid alkaline material, a desulfurization material and a framework material, wherein the mass percentage of the solid alkaline material is 40-70%, the mass percentage of the desulfurization material is 20-50%, and the mass percentage of the framework material is 5-10%.
Further, the solid alkaline material is alkaline aluminosilicate or natural mica powder, the desulfurization material is zinc oxide, and the framework material is diatomite.
The preparation method of the heat conduction oil online alkaline protective agent is characterized by comprising the following preparation steps:
a. uniformly mixing the raw materials or precursors in proportion, adding a cellulose aqueous solution, rolling, granulating and drying; b. Roasting the dried particles; c. And molding the fired particles.
Further, the preparation steps are as follows:
a. uniformly mixing the raw materials or precursors in proportion, adding a cellulose aqueous solution, rolling for 1h, granulating and drying; b. Roasting the dried particles at 300 ℃; c. the fired pellets were shaped and pressed into phi 6 x 6 cylinders.
The invention also provides the application of the heat conduction oil online alkaline protective agent, which is characterized by being used for online control of heat conduction oil acidity and sulfur content.
The heat conduction oil is synthetic aromatic heat conduction oil.
Further, when the protective agent is filled, the ratio of the filling amount to the total volume of the heat conduction oil is 1 to 5 to 1, and the length-diameter ratio of a protective agent bed layer is not lower than 5.
Further, the temperature of the heat transfer oil entering the protective agent bed layer>180 ℃ and space velocity<1.5h -1 。
Further, before the protective agent is not invalid, the acidity of the new heat conducting oil is kept within 0.05mgKOH/g, and the sulfur content is kept within 0.01 percent.
Further, before the protective agent is not invalid, the acidity of the old heat conducting oil is reduced to be within 0.1mgKOH/g, and the sulfur content is kept to be within 0.02 percent.
The invention has the advantages of
The protective agent can be used on line, the acidity of heat transfer oil and the sulfur content of the heat transfer oil are kept or reduced, and the temperature of the heat transfer oil entering a protective agent bed layer>180 ℃ and space velocity<1.5h -1 Preferably space velocity<0.8h -1 Before the protective agent is not invalid, the acidity of the new heat conduction oil can be kept within 0.05mgKOH/g, and the sulfur content can be kept within 0.01 percent; the acidity of the old heat conducting oil can be reduced to be within 0.1mgKOH/g, and the sulfur content can be kept to be within 0.02 percent.
The heat-conducting oil online alkaline protective agent can control the acidity and the sulfur content in heat-conducting oil online, delay the aging of the heat-conducting oil and prolong the service life of the heat-conducting oil.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
Preparation of a protective agent 1: 400g of aluminosilicate, 880g of basic zinc carbonate accounting for 57 percent of ZnO content, 100g of diatomite are taken, 400g of cellulose aqueous solution accounting for 1 percent of ZnO content is added, the mixture is rolled for 1h, granulated, dried, roasted for 4h at 300 ℃, and pressed into phi 6 x 6 cylinders.
Example 2
Preparation of a protective agent 2: 700g of aluminosilicate, 350g of basic zinc carbonate accounting for 57 percent of ZnO content and 100g of diatomite are taken, 350g of cellulose aqueous solution accounting for 1 percent of ZnO is added, the mixture is rolled for 1h, granulated, dried, roasted for 4h at 300 ℃, and pressed into phi 6 x 6 cylinders.
Example 3
Preparation of a protective agent 3: taking 550g aluminosilicate, 700g basic zinc carbonate with ZnO content accounting for 57 percent and 50g diatomite, adding 300g cellulose aqueous solution with 1 percent mass fraction, rolling for 1h, granulating, drying, roasting at 300 ℃ for 4h, and tabletting into phi 6 x 6 cylinders.
Example 4
The heat conducting oil adopts fresh HD-320 alkyl benzene heat conducting oil, organic acid is manually added into the heat conducting oil to adjust the acidity to be slightly lower than about 0.5mgKOH/g, thiophene is added until the sulfur content is about lower than 0.2%, and the heat conducting oil to be abandoned is simulated. The purification device adopts a single-tube non-circulating lower feeding type liquid phase reactor, the loading amount of the protective agent is 50ml, and oil is pumped into a preheater by a metering pump, then enters the purifier and finally is collected by cooling. The feeding temperature is 180 ℃, and the space velocity is 0.8h -1 The decontamination results are shown in the following table:
table 1 protectant 1 decontamination results
Cumulative value of oil, ml Acid value of mgKOH/g Sulfur content% Remarks to note
0-750 0.10 0.02 Effective period of protective agent
750-1000 0.20 0.05 Stage of protective agent failure
1000-1200 0.40 0.10 Stage of protective agent needing to be replaced
1200-1400 About 0.50 About 0.20 Complete failure
Example 5
Protectant 2 the same conditions as in example 4 were used
Table 2 protectant 2 decontamination results
Cumulative value of oil, ml Acid value of mgKOH/g Sulfur content of% Remarks for note
0-500 0.10 0.02 Effective period of protective agent
500-750 0.20 0.02 Stage of protective agent failure
750-900 0.40 0.02 Stage of protective agent needing to be replaced
900-1000 About 0.50 0.10 Complete failure
Example 6
Protectant 3 the same conditions as in example 4 were used
Table 3 protectant 3 decontamination results
Cumulative value of oil, ml Acid value of mgKOH/g Sulfur content of% Remarks for note
0-700 0.10 0.02 Effective period of protective agent
700-900 0.15 0.03 Stage of protective agent failure
900-1200 0.25 0.05 Stage of protective agent needing to be replaced
1200-1400 About 0.50 0.10 Complete failure
Example 7
The method is characterized by simulating online use, connecting a purification tank in a circulating heat conduction oil system in a laboratory, filling 50ml of protective agent 3 into the purification tank, adjusting the rotating speed of a heat conduction oil pump to control the oil airspeed, accelerating the aging of heat conduction oil by adopting fresh HD-320 heat conduction oil and the temperature slightly lower than the upper limit of the rated temperature of the HD-320 heat conduction oil by 320 ℃, wherein the oil airspeed is 1.5h -1 。
Table 4 protectant 3 on-line decontamination results
Time day Acid value of mgKOH/g Sulfur content% Remarks for note
0-40 0.05 0.01 Effective period of protective agent
41-60 0.10 0.02 Stage of protective agent failure
61-70 0.15 0.04 Stage of protectant failure
71-80 0.25 0.06 Stage of protective agent needing to be replaced
81-90 0.35 0.1 Failure of protective agent
Comparative example 1
The conditions are the same as those of example 7, except that the heat transfer oil system is not provided with the protective agent
TABLE 5 Heat transfer oil aging results without protectant
Time, day Acid value of mgKOH/g Sulfur content of% Remarks for note
0-15 0.05 0.01 Stationary phase
16-30 0.10 0.02 Aging period
31-40 0.15 0.04 Aging period
41-45 0.25 0.06 Accelerated aging period
46-50 0.35 0.1 Accelerated aging period

Claims (8)

1. The heat conduction oil online alkaline protective agent is characterized by comprising a solid alkaline material, a desulfurization material and a framework material, wherein the mass percentage of the solid alkaline material is 40-70%, the mass percentage of the desulfurization material is 20-50%, and the mass percentage of the framework material is 5-10%;
the solid alkaline material is alkaline aluminosilicate or natural mica powder, the desulfurization material is zinc oxide, and the framework material is diatomite;
the preparation steps of the heat-conducting oil online alkaline protective agent are as follows:
a. uniformly mixing the raw materials or precursors in proportion, adding a cellulose aqueous solution, rolling, granulating and drying; b. Roasting the dried particles; c. And molding the fired particles.
2. The heat transfer oil online alkaline protective agent according to claim 1, characterized by comprising the following preparation steps:
a. uniformly mixing the raw materials or precursors in proportion, adding a cellulose aqueous solution, rolling for 1h, granulating and drying; b. Roasting the dried particles at 300 ℃; c. the fired pellets were shaped and pressed into phi 6 x 6 cylinders.
3. Use of the on-line alkaline protectant for heat transfer oil according to claim 1, characterized by on-line control of heat transfer oil acidity and sulfur content.
4. The use of the on-line alkaline protectant for heat transfer oil according to claim 3, characterized in that the heat transfer oil is synthetic aromatic heat transfer oil.
5. The use of the online alkaline protective agent for the conduction oil according to claim 3 is characterized in that when the protective agent is filled, the ratio of the filling amount to the total volume of the conduction oil is 1 to 5 to 1.
6. According to the claims3 or 4, the application of the heat conduction oil on-line alkaline protective agent is characterized in that the temperature of the heat conduction oil entering a protective agent bed layer>180 ℃ space velocity<1.5h -1 。
7. The use of the on-line alkaline protective agent for heat transfer oil according to claim 3, characterized in that the acidity of the fresh heat transfer oil is kept within 0.05mgKOH/g and the sulfur content is kept within 0.01% before the protective agent is not deactivated.
8. The use of the on-line alkaline protective agent for heat transfer oil according to claim 3, characterized in that the acidity of the old heat transfer oil is reduced to be within 0.1mgKOH/g and the sulfur content is kept to be within 0.02 percent before the protective agent is not deactivated.
CN202010173383.8A 2020-03-13 2020-03-13 Heat-conducting oil online alkaline protective agent and preparation method and application thereof Active CN113388417B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101760230A (en) * 2008-12-25 2010-06-30 中国石油化工股份有限公司 Method for catalytically deacidifying acid-containing oil
CN102807888A (en) * 2012-08-26 2012-12-05 金堆城钼业股份有限公司 Reformed raw oil desulfurizing agent and preparation method thereof
CN106179375A (en) * 2015-05-07 2016-12-07 中国石油化工股份有限公司 A kind of catalyst for aromatic hydrocarbons Heat Conducting Oil Regeneration and Heat and preparation method

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7763767B2 (en) * 2005-05-04 2010-07-27 Exxonmobil Chemicals Patents Inc. Adsorption process with on-line adsorbent removal
US8815085B2 (en) * 2010-09-24 2014-08-26 Chevron U.S.A. Inc. Process for reducing the total acid number of a hydrocarbon feed

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101760230A (en) * 2008-12-25 2010-06-30 中国石油化工股份有限公司 Method for catalytically deacidifying acid-containing oil
CN102807888A (en) * 2012-08-26 2012-12-05 金堆城钼业股份有限公司 Reformed raw oil desulfurizing agent and preparation method thereof
CN106179375A (en) * 2015-05-07 2016-12-07 中国石油化工股份有限公司 A kind of catalyst for aromatic hydrocarbons Heat Conducting Oil Regeneration and Heat and preparation method

Non-Patent Citations (1)

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