CN1204039C - Method of producing carbon monoxide and hydrogen using methanol and reactor used - Google Patents
Method of producing carbon monoxide and hydrogen using methanol and reactor used Download PDFInfo
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- CN1204039C CN1204039C CNB011428414A CN01142841A CN1204039C CN 1204039 C CN1204039 C CN 1204039C CN B011428414 A CNB011428414 A CN B011428414A CN 01142841 A CN01142841 A CN 01142841A CN 1204039 C CN1204039 C CN 1204039C
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- carbon monoxide
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- methanol
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The present invention relates to a method for preparing carbon monoxide and hydrogen from methanol. In the process of the present invention, CuO/ZnO/Al2O3 group catalysts are adopted, reaction is carried out under the conditions that the methanol liquid space velocity is between 0.1 and 3.0 h<-1>, preferably between 0.5 and 2.0 h<-1>, the reaction temperature is between 160 DEG C and 330 DEG C, and the reaction pressure is between 0 and 3.0MPa, preferably between 0 and 1.0MPa. Simultaneously, the present invention also provides a reaction vessel used for the process.
Description
Invention field
The present invention relates to a kind of method of utilizing methyl alcohol to produce carbon monoxide and hydrogen, adopt CuO/ZnO/Al specifically
2O
3Series catalysts under certain process conditions, utilizes methyl alcohol to produce the gas mixture of carbon monoxide and hydrogen, and separating mixed gas obtains carbon monoxide and hydrogen respectively then.
The invention still further relates to methyl alcohol and produce the reactor that is adopted in carbon monoxide and the hydrogen technology.
Background technology
Carbon monoxide is the important source material in fine chemistry industry, the pharmaceutical industry, and the gas mixture of carbon monoxide and hydrogen can be widely used in industries such as metallurgy and machinofacture.
Chinese patent (ZL96102205.1) discloses a kind of method of preparing hydrogen by methanol vapour transformation, adopts CuO/ZnO/Al
2O
3Series catalysts its objective is and produces hydrogen; The concentration of carbon monoxide is very low in the product, can't separate independent use.Clearly can not utilize this method to produce carbon monoxide.
Summary of the invention
The objective of the invention is on former full scale plant, reactor is simply improved, utilize methyl alcohol under relatively mild condition, to produce the gas mixture of carbon monoxide and hydrogen, carbon monoxide is dense in the gas mixture, obtains carbon monoxide and hydrogen respectively by means such as transformation absorption or low temperature separation processs then.
Technical scheme of the present invention is as follows:
Methyl alcohol enters catalyticreactor after vaporization, at CuO/ZnO/Al
2O
3Under the effect of series catalysts, under certain temperature and pressure, be decomposed into carbon monoxide and hydrogen, product through with material benzenemethanol heat exchange and water quench after, can make carbon monoxide product or carbon monoxide and two kinds of products of hydrogen through means such as transformation absorption or low temperature separation processs again.
Catalyst loading is in reaction tubes, and catalyzer is CuO/ZnO/Al
2O
3Series catalysts is an active ingredient with Cu, and ZnO is an auxiliary agent, with Al
2O
3Be carrier, with co-precipitation or immersion process for preparing and get.The method of preparation is: with nitrate and the ammonium or the alkali-metal carbonate coprecipitation of copper, zinc, aluminium, beat sheet through the washing and drying roasting then; With Al
2O
3With ZnO or use Al separately
2O
3Be beforehand with into strips or chip carrier, flood cupric nitrate and zinc nitrate then, the immersion type catalyzer is made in the drying roasting.Wherein CuO content is 5～60%, and optimum content is 10～50%; ZnO content is 1～35%, and optimum content is 15～30%; Al
2O
3Content is 10～90%, and optimum content is 20～75% (all being weight percentage).
The catalyticreactor of process using of the present invention is a shell and tube reactor, and the reactor synoptic diagram is seen accompanying drawing 1.Material benzenemethanol vapour is walked tube side, and thermal oil is walked shell side; Realize the temperature of beds is controlled by the flow and the temperature of regulating thermal oil.
Reaction conditions is among the present invention: the liquid air speed of methyl alcohol is 0.1～3.0h
-1, 0.5～2.0h preferably
-1Temperature of reaction is 160 ℃～330 ℃; Reaction pressure is generally 0～3.0MPa, preferably 0.1～1.0MPa.
The reactor of methanolysis adopts shell and tube reactor, sees accompanying drawing 1 for details.
In the accompanying drawing 1:
(1): the mouth of pipe 1; (2): the mouth of pipe 2; (3): the mouth of pipe; (4): the mouth of pipe 4.
Methyl alcohol through vaporize overheated after, enter reactor from the mouth of pipe (1), decomposition reaction takes place behind the reaction tubes by loading catalyst, the gas mixture that generates carbon monoxide and hydrogen is discharged by the mouth of pipe (2).With thermal oil controlling reactor temperature, the thermal conductance deep fat is entered by the mouth of pipe (3), is flowed out by the mouth of pipe (4) through shell.Such flow arrangement helps the methanol decomposition reaction in the beds.In the product after the decomposition, carbon monoxide content is 25～30%, can get carbon monoxide product or carbon monoxide and two kinds of products of hydrogen after purifying.
Methyl alcohol is large Chemicals that output is only second to ethene and synthetic ammonia, along with its price of development of technology is to become to falling in steady always; And methyl alcohol is easy to accumulating.So raw materials used being easy to get among the present invention; And the concentration height of carbon monoxide can obtain more CO purpose product after the separation in the gas mixture that the reactor made that technology of the present invention cooperates process to change a social system obtains, and is good in economic efficiency; Simultaneously, in conjunction with the good catalyst activity of using in this technology, long service life, industrialized unit does not have any catalyst deactivation phenomenon after running more than 200 hour.
Embodiment
By means of embodiment effect of the present invention is described below, but the present invention is not limited to following example:
Get cupric nitrate, zinc nitrate, the aluminum nitrate mixed solution of 1 volumetric molar concentration, Cu in the solution: Zn: Al=5: 3.5: 1.5, with volatile salt 70 ℃ of following co-precipitation, after washing, 120 ℃ of oven dry down, 400 ℃ of roastings add graphite then and beat the cylindrical catalyst A. that sheet is made φ 4mm * 5mm
Get above-mentioned catalyzer and pack in the reaction tubes of reactor of the present invention, reaction tubes is of a size of the stainless steel tube of φ 25mm * 3mm * 1200mm.Be 0.5% hydrogen nitrogen mixed gas processing 1 hour with hydrogen content earlier before the running, pressure is 0.5MPa, and the vapour air speed is 300h
-1Elevated temperature to 250 ℃ gradually then, the hydrogen amount of joining in the hydrogen nitrogen mixed gas is increased to hydrogen content 2% gradually, to the outlet of reactor and inlet hydrogen content basic identical till.
To react the bed temperature and rise to 295 ℃.With methanol feedstock vaporization and be superheated to 290 ℃, and being introduced in the reactor, is 1.0h in liquid air speed
-1, pressure is to carry out decomposition reaction under the 0.5MPa.Composition with conventional chromatogram analytical reaction exported product gas sees Table 1.This device is after running 200 hours, and the pressure drop of beds does not obviously increase, and product gas is formed does not have considerable change yet, and activity of such catalysts and good stability are described.
Table 1
*
| Pressure MPa | Bed temperature ℃ | Methanol solution air speed h -1 | Tail gas is formed, % | Unreacted methanol % in the tail gas | ||
| CH 4 | CO 2 | CO | ||||
| 0.5 | 295 | 1.0 | 0.29 | 2.21 | 29.9 | Do not detect |
*All the other are hydrogen to product gas the component in table
Claims (6)
1, a kind of technology of utilizing methyl alcohol to produce carbon monoxide and hydrogen adopts CuO/ZnO/Al
2O
3Series catalysts, the liquid air speed of control methyl alcohol is 0.1～3.0h
-1, temperature of reaction is 160 ℃～330 ℃, reaction pressure is 0～3.0Mpa.
2, technology as claimed in claim 1 is characterized in that CuO/ZnO/Al
2O
3Series catalysts is to adopt the coprecipitation method preparation and get.
3, technology as claimed in claim 1, the content that it is characterized in that CuO in the catalyzer is 5～60%, the content of ZnO is 1～35%, Al
2O
3Content be 10～90%.
4, technology as claimed in claim 3, the content that it is characterized in that CuO in the catalyzer is 10～50%, the content of ZnO is 15～30%, Al
2O
3Content be 20～75%.
5, technology as claimed in claim 1, the liquid air speed that it is characterized in that methyl alcohol is 0.5～2.0h
-1
6, technology as claimed in claim 1 is characterized in that reaction pressure is 0.1～1.0Mpa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011428414A CN1204039C (en) | 2001-12-30 | 2001-12-30 | Method of producing carbon monoxide and hydrogen using methanol and reactor used |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011428414A CN1204039C (en) | 2001-12-30 | 2001-12-30 | Method of producing carbon monoxide and hydrogen using methanol and reactor used |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1429766A CN1429766A (en) | 2003-07-16 |
| CN1204039C true CN1204039C (en) | 2005-06-01 |
Family
ID=4676972
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011428414A Expired - Fee Related CN1204039C (en) | 2001-12-30 | 2001-12-30 | Method of producing carbon monoxide and hydrogen using methanol and reactor used |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1204039C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102688759B (en) * | 2012-05-28 | 2015-03-25 | 中国科学院山西煤炭化学研究所 | Catalyst for hydrogen production from methanol reforming as well as preparation method and application of catalyst |
| CN104892361A (en) * | 2014-03-04 | 2015-09-09 | 中国科学院大连化学物理研究所 | Method for preparing propanol through catalytic conversion of methanol |
| CN104892362A (en) * | 2014-03-04 | 2015-09-09 | 中国科学院大连化学物理研究所 | Method for preparing butanol through catalytic conversion of methanol |
| CN107552058A (en) * | 2017-09-30 | 2018-01-09 | 四川大学 | A kind of microwave heating prepares the methods and applications of methanol cracking catalyst |
-
2001
- 2001-12-30 CN CNB011428414A patent/CN1204039C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1429766A (en) | 2003-07-16 |
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|---|---|---|---|
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| C14 | Grant of patent or utility model | ||
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Owner name: CHINA PETROLEUM & CHEMICAL CORPORATION Free format text: FORMER OWNER: QILU PETROCHEMICAL GROUP CO., CHINA PETROCHEMICAL CORP. Effective date: 20071228 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20071228 Address after: Linzi Zibo District, Shandong province Sinopec Qilu Branch of science and technology Patentee after: Sinopec Corp. Address before: 124 mailbox, Zibo City, Shandong Province Patentee before: Qilu Petrochemical Co., China Petrochemical Group Corp. |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20050601 Termination date: 20131230 |