CN104341266A - Device and method for detecting hydrogen-ester ratio in synthesis gas-to-ethanediol hydrogenation unit - Google Patents

Device and method for detecting hydrogen-ester ratio in synthesis gas-to-ethanediol hydrogenation unit Download PDF

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Publication number
CN104341266A
CN104341266A CN201410567426.5A CN201410567426A CN104341266A CN 104341266 A CN104341266 A CN 104341266A CN 201410567426 A CN201410567426 A CN 201410567426A CN 104341266 A CN104341266 A CN 104341266A
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hydrogen
pipeline
ester ratio
water cooler
hydrogenation
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CN201410567426.5A
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CN104341266B (en
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李红
段巍
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Pujing Chemical Industry Co Ltd
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Anhui Huaihua Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N5/00—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid

Abstract

The invention provides a device for detecting a hydrogen-ester ratio in a synthesis gas-to-ethanediol hydrogenation unit. The device comprises a hydrogenation reactor, a heater, a mixer, a cooler and a collecting tank, wherein an outlet of the mixer is sequentially connected with the heater and the hydrogenation reactor by pipelines, the pipeline from the mixer to the heater is connected with the cooler by virtue of a first pipeline which is provided with a valve, an outlet at the bottom of the cooler is connected with the collecting tank of the decarbonylation buffer tank by virtue of a pipeline, an outlet at the top of the cooler is provided with a second pipeline for discharging at a safe place, and the second pipe is sequentially connected with a thermometer, a pressure meter and a flowmeter in series. The device can be used for accurately working out the hydrogen-ester ratio of hydrogenation reaction, further improving the percent conversion of oxalate, increasing the ethanediol product yield and facilitating the separation and purifying during the refining of the ethanediol product. The invention further provides a method for detecting the hydrogen-ester ratio by virtue of the device disclosed by the invention.

Description

A kind of synthetic gas preparing ethylene glycol hydrogenation unit surveys the device and method of hydrogen ester ratio
Technical field
The invention belongs to ethylene glycol field of industrial production, particularly relate to the device and method that a kind of synthetic gas preparing ethylene glycol hydrogenation unit surveys hydrogen ester ratio.
Background technology
As shown in Figure 1, the hydrogenation unit of existing synthetic gas preparing ethylene glycol, comprise hydrogenator 1 ', well heater 2 ' and mixing tank 3 ', the recycle hydrogen that mixing tank 3 ' comes dimethyl oxalate and hydrogen gas compressor by pipeline and carbonylation surge tank is connected, the outlet of mixing tank 3 ' is connected with hydrogenator 1 ' with well heater 2 ' successively by pipeline, and hydrogenator 1 ' outlet at bottom goes refining purification.
Dimethyl oxalate (the COOCH of technical process mainly by carbonylation unit surge tank of the hydrogenation unit of synthetic gas preparing ethylene glycol 3) 2mixing tank 3 ' is squeezed into through pump, after the recycle hydrogen come with hydrogen gas compressor mixes, heater via 2 ' enters hydrogenator 1 ' after being heated to 200 DEG C, under the effect of the working pressure of 3.0MPa, 215 DEG C of temperature of reaction and hydrogenation catalyst, there is hydrogenation reaction, the crude product ethylene glycol (CH of generation 2oH) 2refined unit is delivered to, separating-purifying and obtain premium grads ethylene glycol after condensation.
Chemical equation is as follows:
(COOCH 3) 2+4H 2→(CH 2OH) 2+2CH 3OH
In hydrogenation reaction, not only to control well reaction service temperature and pressure, also to control well reaction material proportion-hydrogen ester ratio (hydrogen and dimethyl oxalate mol ratio), generally hydrogen ester ratio controls 50 ~ 80.
Because Hydrogenation of Dimethyl Oxalate reaction is a cascade reaction, dimethyl oxalate (COOCH 3) 2methyl glycolate CH is generated with hydrogen reaction 2oHCOOCH 3, its again with hydrogen reaction generating glycol (CH 2oH) 2,
Chemical equation is as follows:
(COOCH 3) 2+2H 2→CH 2OHCOOCH 3+CH 3OH
CH 2OHCOOCH 3+2H 2→(CH 2OH) 2+CH 3OH
If hydrogen ester is more improper than what control, the generation of the side reaction such as Partial hydrogenation or excessive hydrogenation can be caused,
(CH 2OH) 2+H 2→CH 3CH 2OH+H 2O
CH 3CH 2OH+(CH 2OH) 2→HOCH 2CH(OH)CH 2CH 3+H 2O
Partial hydrogenation product ethanol acid methyl esters CH is had like this in hydrogenation reaction 2oHCOOCH 3, excessive hydrogenation product ethanol CH 3cH 2oH and 1,2-butyleneglycol HOCH 2cH (OH) CH 2cH 3deng the generation of by product, not only have impact on the yield of product, is also the difficulty that the separating-purifying of postorder refined unit increases.
Hydrogen ester at present in actual production is than the size can only passing through the variable frequency control amounts of hydrogen of hydrogen compressor, how much concrete hydrogen ester ratio cannot to know, can only by judging whether excessive hydrogenation or Partial hydrogenation to the analysis of hydrogenation reaction product component, carry out adjusting to reach optimum reaction ratio, quite delayed to the regulating and controlling of producing like this.
Summary of the invention
For above-mentioned technical problem, the object of this invention is to provide the device that a kind of synthetic gas preparing ethylene glycol hydrogenation unit surveys hydrogen ester ratio, hydrogen and dimethyl oxalate mol ratio in synthetic gas preparing ethylene glycol hydrogenation unit gas mixture can be measured simply, efficiently, accurately.
The technical solution used in the present invention is:
A kind of synthetic gas preparing ethylene glycol hydrogenation unit surveys the device of hydrogen ester ratio, comprise hydrogenator, well heater, mixing tank, water cooler and receiving tank, the recycle hydrogen that described mixing tank comes dimethyl oxalate and hydrogen gas compressor by pipeline and carbonylation surge tank is connected, the outlet of described mixing tank is connected with hydrogenator with well heater successively by pipeline, described hydrogenator outlet at bottom goes refining purification, pipeline between described mixing tank to well heater is connected with described water cooler by the first pipeline, described first pipeline is provided with valve, the outlet at bottom of described water cooler is connected with removing the receiving tank of carbonylation surge tank by pipeline, described water cooler top exit is provided with the second pipe of safe place emptying, described second pipe is in series with thermometer successively, pressure warning unit and under meter.
Synthetic gas preparing ethylene glycol hydrogenation unit of the present invention surveys the device of hydrogen ester ratio, and wherein, described valve is control valve.
Adopt above-mentioned synthetic gas preparing ethylene glycol hydrogenation unit to survey the method for the measurement device hydrogen ester ratio of hydrogen ester ratio, comprise the following steps:
Open valve, the gas mixture of the unstripped gas of hydrogenation reaction and dimethyl oxalate and hydrogen is through water cooler condensation, making the dimethyl oxalate condensation in gas mixture get off and be recovered in receiving tank, to carrying out weighing measurement G, calculating the mole number n of the dimethyl oxalate that condensation is got off 1, finally deliver to carbonylation barkite surge tank; The uncooled hydrogen got off then measures the temperature T of gas mixture, pressure P and flow F, according to n respectively through thermometer, pressure warning unit and under meter 2=PV/RT, calculates the mole number of hydrogen, and the hydrogen ester so can knowing hydrogenation reaction by the survey calculation of timing compares n=n 2/ (n 1-n 2).
Employing synthetic gas preparing ethylene glycol hydrogenation unit of the present invention surveys the method for the measurement device hydrogen ester ratio of hydrogen ester ratio, and wherein, described gas mixture, through water cooler condensation, controls condensing temperature at 58 ~ 64 DEG C.
Beneficial effect of the present invention:
Synthetic gas preparing ethylene glycol hydrogenation unit provided by the invention surveys the device of hydrogen ester ratio, the hydrogen ester ratio of hydrogenation reaction can be calculated more exactly, like this by the accurate control of temperature of reaction, pressure and hydrogen ester ratio, promote the carrying out of hydrogenation main reaction, suppress the generation of the side reaction such as Partial hydrogenation or excessive hydrogenation, further increase the transformation efficiency of barkite, add the yield of ethylene glycol product, the minimizing of by product simultaneously, also being conducive to the separating-purifying refined, providing guarantee for producing premium grads ethylene glycol.
The present invention adopts synthetic gas preparing ethylene glycol hydrogenation unit to survey the method for the measurement device hydrogen ester ratio of hydrogen ester ratio, hydrogen ester can be controlled exactly than between 50 ~ 80, guarantee carrying out smoothly of hydrogenation main reaction, improve the yield of ethylene glycol product, reduce over the generation of hydrogenation reaction coproduct ethanol and butyleneglycol and Partial hydrogenation byproduct of reaction methyl glycolate simultaneously, be more conducive to the separating-purifying of refining step below.
Accompanying drawing explanation
Fig. 1 is the structural representation of synthetic gas preparing ethylene glycol hydrogenation unit in prior art;
Fig. 2 is the structural representation that synthetic gas preparing ethylene glycol hydrogenation unit of the present invention surveys the device of hydrogen ester ratio.
Below with reference to drawings and Examples, the present invention is described in detail.
Embodiment
As shown in Figure 2, a kind of synthetic gas preparing ethylene glycol hydrogenation unit surveys the device of hydrogen ester ratio, comprise hydrogenator 1, well heater 2, mixing tank 3, water cooler 9 and receiving tank 10, the recycle hydrogen that mixing tank 3 comes dimethyl oxalate and hydrogen gas compressor by pipeline and carbonylation surge tank is connected, the outlet of mixing tank 3 is connected with hydrogenator 1 with well heater 2 successively by pipeline, the outlet at bottom of hydrogenator 1 goes refining purification, pipeline from mixing tank 3 to well heater 2 is connected with water cooler 9 by the first pipeline 5, first pipeline 5 is provided with valve 4, valve 4 is control valve, water cooler 9 outlet at bottom is connected with removing the receiving tank 10 of carbonylation surge tank by pipeline, the top exit of water cooler 9 is provided with the second pipe 11 of safe place emptying, second pipe 11 is in series with thermometer 8 successively, pressure warning unit 7 and under meter 6.
Adopt the present embodiment synthetic gas preparing ethylene glycol hydrogenation unit to survey the method for the measurement device hydrogen ester ratio of hydrogen ester ratio, comprise the following steps:
Open valve 4, the gas mixture of the unstripped gas of hydrogenation reaction and dimethyl oxalate and hydrogen is through water cooler 9 condensation, control condensing temperature at 60 DEG C, dimethyl oxalate condensation in gas mixture is got off and is recovered in receiving tank 10, weighing measurement G is carried out to it, calculates the mole number n of the dimethyl oxalate that condensation is got off 1, finally deliver to carbonylation barkite surge tank; The uncooled hydrogen got off then measures the temperature T of gas mixture, pressure P and flow F, according to n respectively through thermometer 8, pressure warning unit 7 and under meter 6 2=PV/RT, calculates the mole number of hydrogen, and the hydrogen ester so can knowing hydrogenation reaction by the survey calculation of timing compares n=n 2/ (n 1-n 2).
Embodiment 2
Be with the difference of embodiment 1: gas mixture, through water cooler 9 condensation, controls condensing temperature at 58 DEG C.
Embodiment 3
Be with the difference of embodiment 1: gas mixture, through water cooler 9 condensation, controls condensing temperature at 64 DEG C.
Table 1 embodiment hydrogen ester compares measuring result
Test-results shows, is calculated by analysis to measure, and after production technique regulates, hydrogen ester is than substantially all stably controlling between 55 ~ 85.
Above-described embodiment is only be described the preferred embodiment of the present invention; not scope of the present invention is limited; under not departing from the present invention and designing the prerequisite of spirit; the various distortion that those of ordinary skill in the art make technical scheme of the present invention and improvement, all should fall in protection domain that claims of the present invention determines.

Claims (4)

1. the device of a synthetic gas preparing ethylene glycol hydrogenation unit survey hydrogen ester ratio, comprise hydrogenator (1), well heater (2) and mixing tank (3), the recycle hydrogen that described mixing tank (3) comes dimethyl oxalate and hydrogen gas compressor by pipeline and carbonylation surge tank is connected, described mixing tank (3) outlet is connected with hydrogenator (1) with well heater (2) successively by pipeline, described hydrogenator (1) outlet at bottom goes refining purification, it is characterized in that: also comprise water cooler (9) and receiving tank (10), pipeline between described mixing tank (3) to well heater (2) is connected with described water cooler (9) by the first pipeline (5), described first pipeline (5) is provided with valve (4), the outlet at bottom of described water cooler (9) is connected with removing the receiving tank of carbonylation surge tank (10) by pipeline, described water cooler (9) top exit is provided with the second pipe (11) of safe place emptying, described second pipe (11) is in series with successively thermometer (8), pressure warning unit (7) and under meter (6).
2. synthetic gas preparing ethylene glycol hydrogenation unit according to claim 1 surveys the device of hydrogen ester ratio, it is characterized in that: described valve (4) is control valve.
3. adopt the synthetic gas preparing ethylene glycol hydrogenation unit described in claim 1 or 2 to survey the method for the measurement device hydrogen ester ratio of hydrogen ester ratio, it is characterized in that: comprise the following steps:
Open valve (4), the gas mixture of the unstripped gas of hydrogenation reaction and dimethyl oxalate and hydrogen is through water cooler (9) condensation, dimethyl oxalate condensation in gas mixture is got off and is recovered in receiving tank (10), weighing measurement G is carried out to it, calculates the mole number n of the dimethyl oxalate that condensation is got off 1, finally deliver to carbonylation barkite surge tank; The uncooled hydrogen got off then measures the temperature T of gas mixture, pressure P and flow F, according to n respectively through thermometer (8), pressure warning unit (7) and under meter (6) 2=PV/RT, calculates the mole number of hydrogen, and the hydrogen ester so can knowing hydrogenation reaction by the survey calculation of timing compares n=n 2/ (n 1-n 2).
4. synthetic gas preparing ethylene glycol hydrogenation unit according to claim 3 surveys the method for the measurement device hydrogen ester ratio of hydrogen ester ratio, it is characterized in that: described gas mixture, through water cooler (9) condensation, controls condensing temperature at 58 ~ 64 DEG C.
CN201410567426.5A 2014-10-22 2014-10-22 A kind of synthetic gas preparing ethylene glycol hydrogenation unit surveys the device and method of hydrogen ester ratio Active CN104341266B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111732497A (en) * 2020-07-21 2020-10-02 濮阳永金化工有限公司 Device for improving hydrogen-ester ratio and application method

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4088682A (en) * 1975-07-03 1978-05-09 Jordan Robert Kenneth Oxalate hydrogenation process
US4628129A (en) * 1985-02-04 1986-12-09 Union Carbide Corporation Process for the preparation of ethylene glycol
CN101993344A (en) * 2009-08-31 2011-03-30 中国石油化工股份有限公司上海石油化工研究院 Method for preparing ethylene glycol from synthesis gas
CN204174125U (en) * 2014-10-22 2015-02-25 安徽淮化股份有限公司 A kind of synthetic gas preparing ethylene glycol hydrogenation unit surveys the device of hydrogen ester ratio

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4088682A (en) * 1975-07-03 1978-05-09 Jordan Robert Kenneth Oxalate hydrogenation process
US4628129A (en) * 1985-02-04 1986-12-09 Union Carbide Corporation Process for the preparation of ethylene glycol
CN101993344A (en) * 2009-08-31 2011-03-30 中国石油化工股份有限公司上海石油化工研究院 Method for preparing ethylene glycol from synthesis gas
CN204174125U (en) * 2014-10-22 2015-02-25 安徽淮化股份有限公司 A kind of synthetic gas preparing ethylene glycol hydrogenation unit surveys the device of hydrogen ester ratio

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Title
张启云等: "草酸二甲酯加氢合成乙二醇反应的研究", 《石油化工》, vol. 36, no. 4, 31 December 2007 (2007-12-31), pages 340 - 344 *

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Publication number Priority date Publication date Assignee Title
CN111732497A (en) * 2020-07-21 2020-10-02 濮阳永金化工有限公司 Device for improving hydrogen-ester ratio and application method

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