CN1189439C - Alcohol ether material and alcohol hydrocarbon material and synthetic ammonia coproduction process - Google Patents
Alcohol ether material and alcohol hydrocarbon material and synthetic ammonia coproduction process Download PDFInfo
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- CN1189439C CN1189439C CNB021090009A CN02109000A CN1189439C CN 1189439 C CN1189439 C CN 1189439C CN B021090009 A CNB021090009 A CN B021090009A CN 02109000 A CN02109000 A CN 02109000A CN 1189439 C CN1189439 C CN 1189439C
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 164
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 127
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 59
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 55
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 54
- -1 alcohol hydrocarbon Chemical class 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims description 42
- 239000000463 material Substances 0.000 title description 5
- 239000007788 liquid Substances 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 229910052802 copper Inorganic materials 0.000 claims abstract description 22
- 239000010949 copper Substances 0.000 claims abstract description 22
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 79
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000002994 raw material Substances 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 17
- 238000005804 alkylation reaction Methods 0.000 claims description 14
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 230000029936 alkylation Effects 0.000 claims description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000006266 etherification reaction Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 230000001502 supplementing effect Effects 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 230000003009 desulfurizing effect Effects 0.000 claims description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 2
- 239000012495 reaction gas Substances 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 5
- 239000000446 fuel Substances 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000009833 condensation Methods 0.000 abstract 1
- 230000005494 condensation Effects 0.000 abstract 1
- 238000013022 venting Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000007670 refining Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 7
- 238000005265 energy consumption Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
The present invention discloses an alcohol ether object, an alcohol hydrocarbon object thereof and a joint production technology thereof for synthesizing ammonia. The main components of a raw gas for synthesizing ammonia comprise H2, N2, a certain amount of CO and a small quantity of CO2, and what people pursuit is how to convert the CO and the CO2 into an applicable byproduct. The present invention is mainly characterized in that firstly the alcohol ether object is obtained by the alcohol ether reaction by a copper-based catalyst, then the alcohol hydrocarbon object is obtained by the alcohol hydrocarbon reaction by an iron-based catalyst, after cold condensation and separation, the alcohol ether object and the alcohol hydrocarbon object are respectively discharged to corresponding tanks for standby, and at most 10 ppm of CO and CO2 of the remaining gas is conveyed to an ammonia synthesis system. Due to the fact that the alcohol hydrocarbon object can be used as a liquid fuel, the product structure in the ammonia plant is improved, the type of product which is suitable for market is diversified, the content of CH4 entering into the ammonia synthesis system is reduced, and the venting amount during the production is reduced.
Description
A process for preparing alcohol ether, alcohol hydrocarbon and synthetic ammonia features use of both alcohol ether and hydrocarbon and synthetic ammonia.
It is known that in the production of ammonia synthesis plantsAmmonia synthesis requires high feed gas requirements and must be relatively pure hydrogen and nitrogen. While the component range of the general raw material gas is H2+N291％～97％，CO+CO21% -8% of the total weight of the composition, and CH4Ar, etc. Before entering the ammonia synthesis loop, CO and CO must be mixed2And removing the components. The raw material gas is refined to ppm level, otherwise the catalyst for synthesizing ammonia is poisoned and deactivated. The raw material is usually purified by a copper washing method, a deep low methanation method, a methanolation methanation method and a liquid nitrogen washing method. The copper washing method is adopted by more factories in China, the technology is mature, but copper, acetic acid, ammonia and a large amount of steam are consumed, the energy consumption and the material consumption are large, the waste liquid contains heavy metal copper, and the environment is polluted. The liquid nitrogen washing method is mainly suitable for ammonia plants which use coke oven gas as raw material, and although the refining degree of the processed raw material gas is higher, an air separation device is required to be matched with the raw material gas, so that the application range is limited. The deep low-change methanation method has extremely strict limit on the sulfur content in the raw material gas, has large steam consumption, and is not suitable for being used in medium and small fertilizers taking coal as the raw material because of different coal producing areas and different sulfur contents.
As for the refining process of raw gas, the refining process of raw gas of synthetic ammonia, ZL90105545.X, which is invented by Xizhong of Yanchun company in China lake south, and the like, firstly proposes that a fine desulfurization-methanolation-methanation method is used in an ammonia plant to replace a deep low-shift methanation method or a copper washing method in 1990 9 months, and methanol is byproduct. The process method is formally put into production in 1992, has good operation and obvious advantages, the pressure range is only 5-15 MPa, the refining degree is high, the material consumption and the energy consumption are low, and the applicability is wide. The methanol process in the ammonia plant was proposed by Topusolo, Denmark, abroad, late 1991 and planned to be put into operation in 1993 in 1992 in Egypt, but the plant pressure of the process was 22MPa, the water content of methanol was up to 40-50%, and additional heat supply was required to maintain the reaction. Chinese patent ZL93105920.8 'isobaric type methanol and ammonia combined production device', methanol synthesis and ammonia synthesis are at the same high pressure, so the device investment is large, the energy consumption is high, and the refining of raw material gas still needs liquid nitrogen washing, copper washing or methanation.
The above-mentioned traditional methanation method is aimed at making the refining degree of raw material gas meet the requirements for synthetic ammonia, and can prevent the activity of synthetic ammonia catalyst from being reduced due to toxic hazard. The raw material gas has a certain content of CO + CO2And 5-15 ppm level can be achieved through refining. In the refining of raw material gas CH4Will also increase, and CH4Inert gas which does not participate in the reaction in the ammonia synthesis reaction is gradually accumulated in a synthesis ammonia system to form system pressure, when the safety control pressure is reached, a part of mixed gas needs to be discharged, and CH is discharged4At the same time, H in the mixed gas is also mixed2、N2、NH3The effective gas is released at the same time, which is a loss. Therefore, the CH is avoided and reduced as much as possible in the process of synthesizing ammonia4Generation and entry.
China is a country with abundant coal resources and relatively insufficient petroleum, and how to convert coarse solid mineral energy into relatively clean liquid fuel is also a problem which is urgently needed to be solved by the country. However, in the existing ammonia synthesis technology, there is no effective and economical method for removing CO + CO from raw material gas2Mostly into high-quality liquid energy and various fine chemical products, and a very small part into methane.
Therefore, the present invention aims at providing CO-production process of alcohol ether, alcohol hydrocarbon and synthetic ammonia, and the CO-production process can produce CO and CO in material gas with high efficiency and low consumption2The methane is converted into liquid fuel and other fine chemical products, and the generated methane quantity is relatively small. The process includes the first reaction with copper alcohol ether catalyst to produce alcohol ether mixture, water cooling to condense and separate CO and CO accounting for 0.1-0.8 wt%2Reacting the gas with iron series alcohol hydrocarbon catalyst to generate alcohol hydrocarbon mixture, water cooling, condensing and separating to obtain residual H2、N2And a trace of CO + CO2Sent to the synthetic ammonia system. Due to CO and CO2In the alcohol-hydrocarbon process, it becomes possible to condense and separate alcohol-hydrocarbon substances capable of being used as liquid fuels, thereby reducing CH4Thereby reducing ammonia synthesisThe empty amount is reduced, so that the synthetic ammonia is reducedThe consumption of raw material gas, thereby reducing the production cost.
The invention is realized by adopting the following technical means that two alcohol ether reactors are arranged in a synthetic ammonia system device, a copper catalyst is filled in the alcohol ether reactors, the raw material gas is pressurized to be more than 5.0MPa, and CO in the raw material gas are heated to 210-280 DEG C2Most of the total of the components and H2The alcohol ether mixture is generated by the reaction, cooled and condensed into liquid, and the liquid is discharged into a storage tank for later use after separation. The gas after liquid separation is H2、N2And 0.1-0.8% of CO and CO2The gas is fed into an alcohol hydrocarbon reactor filled with iron catalyst to generate alcohol hydrocarbon. Condensing the alcohol hydrocarbon into liquid, and discharging the alcohol hydrocarbon liquid into another storage tank for later use after gas-liquid separation and pressure reduction. The separated gas is mainly H2、N2And a small amount of CH4And less than or equal to 10ppm of CO + CO2Sending the ammonia to a synthetic ammonia system for producing ammonia, condensing the ammonia into liquid ammonia, separating the liquid ammonia, supplementing pressure and gas, then entering a synthetic tower for reaction, and circulating the steps. The reactors are connected with each other into a system through pipelines, valves and a circulator.
The structural and process features of the present invention are described in detail below with reference to the accompanying drawings and examples.
Drawings
FIG. 1 is a process flow chart of the invention with the raw material gas CO being more than or equal to 1.8%.
FIG. 2 is a process flow chart of the invention in which the CO content of the raw material gas is less than or equal to 1.8%.
Referring to fig. 1, the overall system includes: comprises an alcohol ether reactor A (1), an alcohol ether reactor B (2), an alcohol hydrocarbon reactor C (9), gas heat exchangers (3), (4) and (10), water coolers (5), (6) and (11), gas-liquid separators (7), (8) and (13), a liquid ammonia cooler (12), a two-way valve (A)1)、(A2)、(A3)、(B1)、(B2)、(B3)、(C1)、(C2)、(J1)、(J2)、(J3) A tee joint (M),circulator (CM)1)、(CM2) The composition is as follows. The alcohol ether reactor A (1) is connected in series with a heat exchanger (3), a water cooler (5) and a gas-liquid separator (7), the alcohol ether reactor B (2) is connected in series with a heat exchanger (4), a water cooler (6) and a gas-liquid separator (8), and the alcohol hydrocarbon reactor C (9) is connected in series with a heat exchanger (10), a water cooler (11), a liquid ammonia cooler (12) and a gas-liquid separator (13). The systems are communicated with each other through pipelines, valves and a circulator, the flow direction is controlled by the valves, and the circulator is used for temperature rise reduction of the catalyst and temperature control in the reaction process. The invention is mainly characterized in thatOne characteristic is that two parallel alcohol ether reactors (1) and (2) are arranged in the whole system. Containing H in the feed gas2、N2、CO、CO2In the composition range of H2+N291％～97％，CO+CO21-8%, desulfurizing the raw material gas to reduce the total sulfur content to below 1ppm, and pressurizing to above 5 MPa. In the structural design and production operation of the product, the following conditions exist according to the requirements:
1. if the designed ammonia/alcohol ether ratio is small, the CO content in the feed gas is more than 4 percent, and the parallel operation is adopted: the raw material gas firstly enters an alcohol ether reactor, a copper catalyst taking copper, zinc, aluminum and rare earth as main bodies is filled in the alcohol ether reactor, alcohol ether reaction is carried out in the alcohol ether reactor, and the process route is as follows: main pipeline of raw material gas, respectively passing through valve (A)1)、(B1) The heat exchangers (3) and (4) are preheated to 210-220 ℃, enter the alcohol ether reactors (1) and (2) and react at the temperature of 210-290 ℃ to generate an alcohol ether mixture, hot gas after reaction passes through the heat exchangers (3) and (4) from the inside of the tube and is cooled to 70-90 ℃, alcohol and ether in the gas are condensed into liquid after passing through the water coolers (5) and (6), and the content of the ether in the liquid is 30-40%. The alcohol ether liquid mixture is separated by separators (7) and (8) and discharged to a storage tank for standby, and the gas passes through a valve (A)2)、(B2) Joined at a tee (M) via a valve (C)1) Into an alcohol alkylation reactor (9).
CO + CO in raw material gas after alcohol etherification reaction2Reducing to 0.1% -0.8%, passing through valve (C)1) Preheating to 180-210 ℃ by a heat exchanger (10), entering an alcohol alkylation reactor (9), loading an iron-based alcohol alkylation catalyst in the alcohol alkylation reactor (9),the main components of the catalyst are iron, copper, cerium, potassium, aluminum and the like, the reaction is carried out at the temperature of 200-300 ℃, alcohols, hydrocarbons and methane are generated through the reaction, the reaction product is cooled to 70-90 ℃ through a heat exchanger (10) and is cooled to 35-40 ℃ through a water cooler (11), the mixture of the alcohols and the hydrocarbons and water vapor are condensed into liquid, the gas is continuously cooled to 5 ℃ through an ammonia cooler (12), the content of saturated vapor of the gas is reduced to the minimum, the liquid mixture of the alcohols, the hydrocarbons and the water is separated through a separator (13), the alcohol and the hydrocarbon in the liquid account for 40-50 percent, and at the moment, CO and CO in the gas are2The sum of the contents is reduced to below 10ppm to meet the requirement of ammonia synthesis, and the gas is sent to the ammonia synthesis process.
CO and CO in raw material gas2Mainly of and H2The reaction is carried out to generate alcohol ether and alcohol hydrocarbon, and the chemical reaction formula is as follows:
alcohol etherification:
alcohol alkylation:
the above process flow can be expressed by the following simple arrow:
the feed gas valve (A1) is opened → the heat exchanger (3) → the alcohol ether A reactor (1) → the heat exchanger (from the inside of the pipe) (3) → the water cooler (5) → the gas-liquid separator (7).
Opening of raw material gas valve (B1) → heat exchanger (4) → B alcohol ether reactionVessel (2) → heat exchanger (from inside of tube) (4) → water cooler (6) → gas-liquid separator (8) → (a)2)、(B2) Valve opening → converging at tee joint (M) → valve (C)1) Open → alcohol hydrocarbon systems.
The technological process of the alcohol alkylation reaction is briefly described as follows:
alcohol etherification gas → (C)1) Valve opening → heat exchanger (10) preheat to 180 ℃ -210 ℃ → alcohol hydrocarbon reactor (9) generate alcohol hydrocarbon and methane → heat exchanger (10) cool to 70 ℃ -90 ℃ → water cooler (11) cool to 35 ℃ -40 ℃ alcohol and hydrocarbon condense to liquid → liquid cooler (12) cool to 5 ℃ → gas-liquid separator (13) separate liquid alcohol hydrocarbon and water mixture, liquid alcohol hydrocarbon approximately accounts for 40% -50%, CO + CO in gas2Down to below 10ppm → ammonia synthesis system.
When the catalyst in one alcohol ether reactor is in the aging stage, a series flow scheme can be used, as indicated by the arrow flow direction:
raw gas → valve (A)1) Opening, (B)1) Closing → heat exchanger (3) → A alcohol ether reactor (1) → heat exchanger(3) → water cooler (5) → gas-liquid separator (7) → valve (A)3) Opening (A)2) Closing → heat exchanger (4) → B alcohol ether reaction (2) → heat exchanger (4) → water cooler (6) → gas-liquid separator (8) → valve (B)3) Off (B)2) Open → three-way (M) → valve (C)1) Open → C alcohol alkylation system (9).
2. In the product design, if the ammonia/alcohol ether is relatively large, i.e. the content of CO in the feed gas is relatively low (e.g. 1.8-4%), a single-tower system is adopted, and the flow diagram of the arrow is as follows:
as single run with a reactor (1):
raw gas → valve (A)1) On, (B)1) Closing → heat exchanger (3) → a alcohol ether reactor (1) → heat exchanger (3) → water cooler (5) → gas-liquid separator (7) valve (a) at this time3)、(B2)、(B3) Off, (A)2) Open → three-way (M) → valve (C)1) Open → alcohol alkylation system (9).
As a single run with the B reactor (2):
raw gas → valve (A)1) Off, (B)1) Open → heat exchanger (4) → B alcohol ether reactor (2) → heat exchanger (4) → water cooler (6) → gas-liquid separator (8) at this time valve (A)3)、(A2)、(B3) Off, (B)2) Open → three-way (M) → valve (C)1) Open → alcohol alkylation reaction system (9).
3. If the ammonia/alcohol ether ratio is large, namely the CO content in the feed gas is below 1.8 percent, the alcohol ether reaction and the alcohol hydrocarbon reaction are carried out in the same reactor, the process flow and the equipment can be simplified, namely the upper part of the reactor is filled with the alcohol ether catalyst, and the lower part of the reactor is filled with the alcohol hydrocarbon catalyst, and the process flow is shown as the figure 2:
raw material gas → valve (d)1) Opening, (J)5) Off → heat exchanger (14) → reactor (D) → heat exchanger (14) → water cooling (15) → ammonia cooling (16) → separators (17), (J4) off → on (D2) → transfer synthesis.
4. The catalysts used in the present invention are of two families:
the alcohol etherification catalyst is copper system, which uses copper, zinc, aluminum and rare earth as main body, and its atomic ratio is Cu, Zn and Al 2-3: 1: 2-2.5, CeO2Is 3% of Al2O3As active Al2O3. The overall dimensions of the catalyst are: a cylindrical shape of phi 5 multiplied by 5, a spherical shape of phi 3 to phi 4, a specific gravity of the catalyst of 1.3 to 1.5g/ml, and the catalyst is used for CO and CO2The conversion of (A) increases with increasing pressure, the reaction temperature being between 210 ℃ and 290 ℃. The catalyst is in oxidation state when leaving the factory, and after being loaded into a reactor, H is needed2、N2Gas is activated and reduced to metallic state.
The alcohol alkylation catalyst is iron system, and its main components are iron, aluminium, potassium, copper and cerium. Wherein Fe3O480-85 percent of CaO, 2-3.5 percent of Al2O32.5％～3.5％，K20.8 to 2 percent of O and CeO20.5-2.5% of CuO and 3-4% of CuO. The catalyst is in oxidation state when leaving factory, and after being loaded into a reactor, the catalyst must be reduced to metal state to have activity. The catalytic performance of the catalyst is increased along with the increase of the pressure, and the optimal reaction temperature is 200-300 ℃.
In order to control and adjust the content of the ether, the proportion of copper in the alcohol ether catalyst is adjusted, so that a methanol-based product with the ether content of less than 0.5 percent can be obtained, otherwise, the proportion of copper in the alcohol ether catalyst is reduced, the content of aluminum oxide is increased, and an alcohol ether mixture with the ether content of 5-30 percent can be obtained.
In order to control the reaction temperature and the temperature rise reduction of the whole system, the invention designs a system circulator so as to facilitate the temperature rise reduction of the catalyst of each reactor. Three reaction systems of the whole device, namely two alcohol ether systems and one alcohol hydrocarbon system, can be simultaneously heated and reduced. During production, if CO and CO entering the system are met2High content, fast temperature rise, and can open the circulator to control the temperature if entering the alcohol alkylation reaction system2When the content is less than 0.4 percent, the self-heating reaction can not be carried out, an external heat supplementing mode is adopted, electric furnace heat supplementing is carried out in a reactor, or superheated steam and other high-temperature gas are used for heating outside a tower, so that the reaction gas reaches the minimum temperature required by the reaction.
The heating reduction process flow is as follows:
the alcohol ether system is heated and reduced first, and the alcohol hydrocarbon system is heated and reduced later.
a. Two alcohol ether systems are connected in parallel for heating reduction, and the process flow is as follows:
closing valve (C)1)、(A3)、(B3) Opening two-way valve (J)1)、(J2)、(A2)、(B2) open-Cycle Machine (CM)1) The reducing gas passes through a two-way valve (J)1) → parallel running through valve (A)1)、(B1) Respectively flowing into an alcohol ether reactor (1) A and an alcohol ether reactor (2) B of the alcohol ether system through a valve (A)2)、(B2) → convergence in three-way (M) → passing through two-way valve (J)2) Entering into a Circulator (CM)1) And (4) circulating until the required temperature is reached.
b. An alcohol ether reactor is independently heated for reduction, and the reactor A (1) is taken as an example for illustration:
closing valve (B)1)、(B2)、(B3) → opening valve (A)1)、(A2)、(J2) open-Cycle Machine (CM)1)、Two-way valve (J)1) Reducing gas passing through gas valve (J)1)、(A1) → heat exchanger (3) → A alcohol ether reactor (1) → heat exchanger (3) → water cooler (5) → gas-liquid separator (7) → passing valve (A)2) Three-way valve (M) and valve (J)2) → Circulator (CM)1) And an inlet for circulating according to the route.
c. Alcohol hydrocarbon system heating system:
closing valve (J)2)、(C2) → opening valve (C)1)、(J3) Open Cycle Machine (CM)2) → alcohol back gas from tee (M) → trans valve (C)1) And the circulation is carried out in the way that heat exchanger (10) → alcohol alkylation reactor (9) → heat exchanger (10) → water cooler (11) → ammonia cooler (12) → gas-liquid separator (13) → valve (J3), circulator (CM2) inlet, and so on.
d. The alcohol ether reaction and the alcohol hydrocarbon reaction share a reactor heatingsystem:
the alcohol ether catalyst and the alcohol hydrocarbon catalyst are filled in a reactor, and the temperature rise (reduction) process is as follows:
closing valve (d)2) Opening valve (J)4)、(J5) Open Cycle Machine (CM)3) Raw gas → valve (d)1) → heat exchanger (14) → reactor (D) → heat exchanger (14) → water cooler (15) → ammonia cooler (16) → separator (17) → valve (J4) → Circulator (CM)3) → separator (18) → valve (J)5) → valve (d)1) Thus forming a cycle.
One of the other important characteristics of the invention is that the pressure application range is wide, the pressure can be carried out at 5-40MPa, and the alcohol etherification and the alcohol alkylation can be designed to be isobaric or different pressures. The higher the reaction pressure, the faster the reaction speed, but the higher the pressure, the higher the compression energy consumption, the higher the equipment requirement and the larger the investment. When CO in the raw material gas is high and the yield of the alcohol ether mixture is high, the alcohol ether reaction is carried out at a low pressure, for example, the reaction is carried out at 5-15 MPa, and the pressure of the alcohol hydrocarbon reaction can be equal to that of ammonia synthesis and is carried out at 15-40 MPa. On the contrary, when the CO of the raw material gas is low, the reaction of the alcohol ether and the alcohol hydrocarbon can be carried out with ammonia synthesis under the equal pressure of 10-40 MPa.
Claims (5)
1. A process for preparing alcohol ether, alcohol hydrocarbon and synthetic ammonia includes such steps as providing: two parallel alcohol ether reactors (1) and (2), an alcohol hydrocarbon reactor (9), gas-gas heat exchangers (3), (4) and (10), water coolers (5), (6) and (11), gas-liquid separators (7), (8) and (13), a liquid ammonia cooler (12) and a two-way valve (A) are arranged1)、(A2)、(A3)、(B1)、(B2)、(B3)、(C1)、(C2)、(J1)、(J2)、(J3) Three-way valve (M) and Circulator (CM)1)、(CM2) The system consists of an alcohol ether reactor A (1) which is connected with a heat exchanger (3), a water cooler (5) and a gas-liquid separator (7) in series, an alcohol ether reactor B (2) which is connected with a heat exchanger (4), a water cooler (6) and a gas-liquid separator (8) in series, an alcohol hydrocarbon reactor C (9) which is connected with a heat exchanger (10), a water cooler (11), a liquid ammonia cooler (12) and a gas-liquid separator (13) in series, wherein the reactor systems are connected and communicated with each other through pipelines, valves and circulators to control the operation of the reactor systems, and the system contains2、N2、CO、CO2、CH4Ar as the feed gas, wherein H2+N291％-97％、CO+CO21% -8%, desulfurizing to reduce the total sulfur content to below 1ppm, pressurizing to above 5MPa, and passing through valve (A)1)、(B1) The heat exchangers (3) and (4) are preheated to 210-220 ℃, the mixture enters alcohol ether reactors (1) and (2) filled with alcohol ether catalysts in parallel, alcohol ether reaction is carried out at the temperature of 210-290 ℃ to generate alcohol ether mixture, hot gas after the reaction is cooled to 70-90 ℃ through the heat exchangers (3) and (4), alcohol and ether in the gas are condensed into liquid after passing through water coolers (5) and (6), the ether content in the liquid reaches 5-30 percent, the separated mixed liquid is discharged to a storage tank through separators (7) and (8), and the gas passes through a valve (A)2)、(B2) Collected at the tee joint (M) and passes through the valve (C)1) The heat exchanger (10) is preheated to 180-210 ℃, and CO in the gas after the etherification are carried out at the moment2Reducing to 0.1-0.8%, entering into an alcohol hydrocarbon reactor (9) filled with iron catalyst, performing alcohol hydrocarbon reaction at 200-300 deg.C to produce alcohol and hydrocarbon mixtureA compound andmethane is cooled to 70-90 ℃ by a heat exchanger (10), cooled to 35-40 ℃ by a water cooler (11), condensed into liquid by alcohol, hydrocarbon mixture and water vapor, continuously cooled to 5 ℃ by an ammonia cooler (12), separated into liquid alcohol, hydrocarbon and water mixture by a gas-liquid separator (13), decompressed and discharged into a liquid storage tank, and CO in the gas2Sum of less than or equal to 10ppm, H2、N2And methane passing valve (C)2) Entering an ammonia synthesis system, carrying out ammonia synthesis reaction in an ammonia synthesis tower to generate ammonia, condensing the ammonia into liquid ammonia by cooling, separating the liquid ammonia, supplementing pressure and air, then entering the synthesis tower for reaction, and circularly operating in the way.
2. The process for coproducing alcohol ether and alcohol hydrocarbon and synthetic ammonia according to claim 1, wherein the following conditions are satisfied depending on the content of CO in the feed gas:
a. when the CO content in the feed gas is more than 4 percent, the two alcohol ether systems are operated in parallel or in series in the production operation process; when the catalyst of two alcohol ether reactors (1) and (2) and one of the reactors is in the aging period, the series operation is adopted, and the process flow is as follows:
raw gas → valve (A)1) Opening, (B)1) Closing → A alcohol ether reactor (1) → heat exchanger (3) → water cooler (5) → separator (7) → valve (A)3) Opening (A)2) Closing → heat exchanger (4) → B alcohol ether reactor (2) → heat exchanger (4) → water cooler (6) → separator (8) valve (B)2) Opening (B)3) Closed → three-way (M) → valve (C)1) Open → C alcohol hydrocarbon reactor (9);
b. when CO in the raw material gas is 1.8-4%, only one alcohol ether reactor is adopted and one alcohol hydrocarbon reactor is connected in series, and the process flow is as follows:
raw gas → valve (A)1)、(B1) Closing → A alcohol ether reactor → heat exchanger (3) → water cooler (5) → separator (7) → valve (A)3) Off, (A)2) Opening, (B)2) Off → T-junction (M) → (J)2) Off, (C)1) Open → heat exchanger (10) → alcohol hydrocarbon reactor (C) → heat exchanger (10) → water cooler (11) → ammonia cooler (12) → separator (13) → (C)2) Opening, (J)3) Guan → ammonia synthesis；
c. When the CO content in the raw material gas is below 1.8 percent, alcohol ether reaction and alcohol hydrocarbon reaction are carried out in the same reactor, namely one end of the reactor is filled with an alcohol ether catalyst, and the other end is filled with an alcohol hydrocarbon catalyst, and the process flow is as follows:
raw material gas → valve (d)1) Opening, (J)5) Closed → heat exchanger (14) → reactor (D) → heat exchanger (14) → water cooling (15) → ammonia cooling (16) → separator (17), (J)4) Off → Send to synthesize.
3. The process for coproducing alcohol ether and alcohol hydrocarbon and synthetic ammonia according to claim 1, which is characterized in that: the catalyst for alcohol etherification is copper system, which uses copper, zinc, aluminium and rare earth as main body, and its atomic ratio is Cu, Zn and Al is 2-3: 1: 2-2.5, CeO2Is 3% of Al2O3As active Al2O3The catalyst is charged into the reactor and then needs to be H2、N2The gas is activated and reduced to metallic state, the reaction temperature is 210-290 ℃, the alcohol alkylation catalyst is an iron system, and the main components are iron, aluminum, potassium, copper and cerium, wherein Fe3O480-85 percent of CaO, 2-3.5 percent of CaO and K2O 0.8％-2％，Al2O32.5％-3.5％，CeO20.5-2.5 percent of CuO 3-4 percent of CuO, and H is needed when the catalyst is used2、N2The gas is reduced to metallic state, and the reaction temperature is 200-300 ℃.
4. The process for coproducing alcohol ether and alcohol hydrocarbon and synthetic ammonia according to claim 1, which is characterized in that: is provided with a system Circulator (CM)1) And (CM)2) Is convenient for the temperature rise reduction of the catalysts of the three reaction systems and the CO entering the system2When the content is less than 0.4 percent and the self-heating reaction can not be carried out, an electric heater in the reactor or superheated steam or other high-temperature gas is used for heating outside the tower, so that the reaction gas reaches the minimum temperature required by the reaction.
5. The process for coproducing alcohol ether and hydrocarbon and synthetic ammonia according to claim 1, wherein the reaction pressure is in the range of 5 to 40 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021090009A CN1189439C (en) | 2001-10-19 | 2002-04-16 | Alcohol ether material and alcohol hydrocarbon material and synthetic ammonia coproduction process |
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| Application Number | Priority Date | Filing Date | Title |
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| CN01128688.1 | 2001-10-19 | ||
| CN01128688 | 2001-10-19 | ||
| CNB021090009A CN1189439C (en) | 2001-10-19 | 2002-04-16 | Alcohol ether material and alcohol hydrocarbon material and synthetic ammonia coproduction process |
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| CN1189439C true CN1189439C (en) | 2005-02-16 |
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| AU2003221277A1 (en) | 2003-02-19 | 2004-09-09 | Feng Yu Dai | A joint process for preparing alcohol-ether, alcohol- hydrocarbon and synthesising ammonia |
| CN100339298C (en) * | 2004-05-08 | 2007-09-26 | 吕仲明 | Non-isostatic alcoholization alkylation process for purifying raw gas for ammonia synthesis |
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