CN100551535C - A kind of catalst for synthesis of methanol and preparation method thereof - Google Patents
A kind of catalst for synthesis of methanol and preparation method thereof Download PDFInfo
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- CN100551535C CN100551535C CNB2005100953431A CN200510095343A CN100551535C CN 100551535 C CN100551535 C CN 100551535C CN B2005100953431 A CNB2005100953431 A CN B2005100953431A CN 200510095343 A CN200510095343 A CN 200510095343A CN 100551535 C CN100551535 C CN 100551535C
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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
Abstract
The present invention relates to a kind of with CO, CO
2And H
2The Catalysts and its preparation method of synthesizing methanol.Be the metal oxide of Cu/Zn/Al three components coexistence, its active constituent weight ratio is Cu30～70%, Zn30～60%, and Al3～15%, catalyst adopt the preparation of co-precipitation mixing method.It is good that catalyst provided by the present invention has a low temperature active than Cu/Zn/Al product, the initial activity height, Heat stability is good, heat-resisting back is active improves 20%～30%, methyl alcohol selectivity height, and the life-span can prolong 2～4 months, be particularly useful for joining pure production technology.
Description
Technical field:
The present invention relates to a kind ofly be used for CO CO
2And H
2The Catalysts and its preparation method of synthesizing methanol.
Background technology:
Methyl alcohol is a kind of important Organic Chemicals, and it is widely used for aspects such as formaldehyde, ethanol, acetic acid, methyl tertiary butyl ether(MTBE), medicine, agricultural chemicals.In recent years, along with the exploitation of C1 chemistry, the application of methyl alcohol is constantly expanded, and its demand is also in continuous expansion, and the development methanol industry has good prospect.At first, methyl alcohol is all taken from the dry distillation of wood.CO, CO
2And H
2It is nineteen twenty-three that synthesizing methanol starts from, and at that time, high-pressure process is all adopted in synthesizing methanol industry, and (300 ℃～400 ℃, at the beginning of 25Mpa-30MPa) catalyst was the ZnO/Cr2O3.50 age, Poland at first used ternary CuO/ZnO/Al
2O
3Catalyst is studied in synthesizing methanol. compares with the ZnO/Cr2O3 catalyst, copper-based catalysts has low temperature, low pressure and advantage of high activity, but to poisonous substances and hot extremely sensitive such as sulphur. along with the development of gas purification technique and the further raising of catalyst heat endurance, the sixties, the application of copper-based catalysts entered a new developing stage. and China is also developed by Research Institute of Nanjing Chemical Industry Group the beginning of the seventies at the end of the sixties and is applied to the exclusive technologic C207 connection of the connection alcohol alcohol catalyst of China, the producer that produces this type catalyst now is numerous, but there is improvement at the production technology end in decades, expose this catalyst initial activity height, but the fast characteristics of activity decay.
Summary of the invention:
Purpose of the present invention is intended to develop a kind of high activity and the good synthetic copper-based catalysts of methyl alcohol of activity stability.
The present invention is achieved like this: Preparation of catalysts, adopt the co-precipitation mixing method. and the Cu of metering, the soluble-salt of Zn is made into mixed liquor, under agitation is added to 70 ℃～80 ℃ Na
2CO
3In the solution, control pH=7.0～7.5 are terminal point, at 70 ℃～80 ℃, stop to add thermal agitation behind especially 76 ℃～78 ℃ aging 0.5h～1h, arrive no NO with deionized water washing sediment
3 -, add the AL (OH) that measures and carry out activation processing with the BAS of 1%-8%
3Powder, and stirring 15～30 minutes, filtration is drained, and 105 ℃～120 ℃ oven dry, to pulverize after the cooling be 40 orders～60 orders, in 350 ℃ of calcining 1.5h～2.5h, fine ground then is 60 orders～100 orders, adds a small amount of graphite and deionized water, mixing, compression molding.
Catalyst with method for preparing is Cu, Zn, and the metal oxide of AL coexistence, its active constituent weight ratio Cu is 30`～70%, is preferably 40～60%; Zn is 20～50%, is preferably 25～45%; AL is 5～15%, is preferably 6～10%.The raw material that catalyst uses: Cu, Zn
+Be selected from no CL
-No SO4
2Soluble-salt, nitrate especially; AL is selected from the AL (OH) of powder (160 orders～320 orders)
3Soda ash is selected from content 〉=98.5%, the Na of CL-≤0.1%
2CO
3
Catalyst activation (reduction) is adopted low H at fixed bed reactors
2Concentration (H
2/ N
2=3/97, V/V) reduction 16h～20h, reduction temperature is 230 ℃～240 ℃.
Following method is adopted in the catalyst activity evaluation:
The methyl methanol syngas detection system: reactor is five groove towers, CO, CO
2Use infrared CO, CO respectively
2Analyzer detects.Methanol feedstock gas contains CO2.5%～4.5%, CO
20.8%～1.1%, H
2＞75%, reaction pressure 10.0MPa, air speed 2 * 10
4h
-1, 230 ℃～250 ℃ of determination of activity temperature heat-resistingly are treated to 450 ℃ of 5h, sample granularity 16 orders～40 orders, and sample device 4ml. catalyst activity is with CO conversion ratio (%); CO
2Conversion ratio (%) expression.Table 1 illustrates two kinds of active contrasts in the heat-resisting front and back of catalyst, and NC-66 represents the laboratory sample of one of the present invention's prescription, and NC-66 refers to the sample through scale-up, and C207 is an industry connection alcohol catalyst.See that from table 1 NC-66 is after heat-resisting processing, the CO conversion ratio is 74%, and is higher 7 percentage points than C207.
Table 1: two kinds of active comparing results in the heat-resisting front and back of methanol synthesis catalyst
Catalyst of the present invention relatively has following characteristics with similar Cu/Zn/Al catalyst:
(1) active good. the active temperature scope is 200 ℃～290 ℃, low 5 ℃～10 ℃ of optimal reaction temperature.
(2) better heat stability.In connection raw polyol gas 450 ℃ heat-resisting 5 hours, its CO conversion ratio exceeds 3～7 percentage points.
(3) methyl alcohol selectivity height.Methanol content improves 2%～5% in the thick methyl alcohol; Methanol yield amplification can reach 10%～30%.
(4) long service life.Can prolong 2～4 months.
The specific embodiment:
The present invention is further described below by embodiment.
Embodiment 1
(1) joins mixed liquor.Get 1.0M Cu (NO
3)
2750ml, 1.0M Zn (NO
3)
2750ml is mixed in the 2000ml beaker.
(2) neutralization.Get 3000ml 0.25M Na
2CO solution places the 5000ml beaker to be heated to 80 ℃, under stirring condition, (1) mixed liquor is added to Na with the speed of 200ml/min
2CO
3In the solution, be terminal point when PH=7.2, wearing out stopped to add thermal agitation after 0.5 hour.
(3) washing.Treat (2) post precipitation, clean (with 70 ℃ of deionized waters) sediment to there not being NO with gradient method
3 -
(4) 12.5g Al (OH)
3Powder elder generation carries out activation processing with 3% BAS, again to going in the sediment and stirring 20min.
(5) suction filtration, 110 ℃ of oven dry are pulverized, 350 ℃ of calcining 2h.
(6) compression molding.(4) gained mixed oxide is added a small amount of graphite and water, mix compressing tablet thoroughly.It is standby that fragmentation is screened into 16 orders～40 orders.
Above-mentioned catalyst is CO/H at gas ingredients
2/ CO
2/ N
2=12/70/3/15, pressure is 10.0Mpa, and air speed is 2 * 10
4h
-1, reaction temperature is that initial activity is (CO, CO under 250 ℃ the laboratory evaluation condition
2Conversion ratio %); Heat-resisting back active (CO, CO
2Conversion ratio %) as table 2:
Embodiment 2 to 4 is except that composition of raw materials, and all the other conditions and method for making are with example 1. result such as tables 2
Table 2: the evaluation result of different formulations
Claims (3)
1, a kind of preparation method of catalst for synthesis of methanol is characterized in that adopting the co-precipitation mixing method, and the Cu of metering, the solubility nitrate of Zn is made into mixed liquor, under agitation is added to 70 ℃～80 ℃ Na
2CO
3In the solution, control pH=7.0～7.5 are terminal point, stop to add thermal agitation behind 70 ℃～80 ℃ aging 0.5h～1h, arrive no NO with deionized water washing sediment
3 -, add the Al (OH) that measures and carry out activation processing with the BAS of 1%-8%
3Powder, and stirring 15～30 minutes, filtration is drained, and 105 ℃～120 ℃ oven dry, to pulverize after the cooling be 40 orders～60 orders, in 350 ℃ of calcining 1.5h～2.5h, fine ground then is 60 orders～100 orders, adds a small amount of graphite and deionized water, mixing, compression molding.
2, Preparation of catalysts method according to claim 1, its feature is at Al (OH)
3Powder elder generation carries out activation processing with 3% BAS.
3, Preparation of catalysts method according to claim 1 is characterized in that aging temperature is 76 ℃～78 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100953431A CN100551535C (en) | 2005-11-09 | 2005-11-09 | A kind of catalst for synthesis of methanol and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100953431A CN100551535C (en) | 2005-11-09 | 2005-11-09 | A kind of catalst for synthesis of methanol and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1962063A CN1962063A (en) | 2007-05-16 |
| CN100551535C true CN100551535C (en) | 2009-10-21 |
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ID=38081387
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531819A (en) * | 2010-12-30 | 2012-07-04 | 中国科学院大连化学物理研究所 | Method for preparing methane and methanol by using synthesis gas |
| CN102407115A (en) * | 2011-09-26 | 2012-04-11 | 上海应用技术学院 | Catalyst for preparation of lower alcohols by synthetic gas, preparation method and application |
| CN105727959B (en) * | 2014-12-11 | 2018-08-07 | 中国石油化工股份有限公司 | A method of preparing methanol synthesis catalyst using micro passage reaction |
| CN110624599B (en) * | 2018-06-25 | 2022-08-23 | 中国石油化工股份有限公司 | Methanol synthesis catalyst and preparation method thereof |
| CN111530467B (en) * | 2019-10-23 | 2021-02-05 | 宁夏大学 | Carbon modified copper-based catalyst and preparation method and application thereof |
-
2005
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Address after: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee after: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Address before: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee before: Nanhua Group Research Institute |
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