CO-PRODUCTION OF METHANOL, AMMONIA AND UREA

Abstract

Process for the co-production of methanol and ammonia together with urea production from a hydrocarbon feed without venting to the atmosphere carbon dioxide captured from the methanol or ammonia synthesis gas and without using expensive air separation units and water gas shift. Carbon dioxide removal from flue gas from reforming section to convert partially or fully all ammonia into urea. Synergi of having methanol, ammonia and urea production to produce coating material for the urea production.

Claims

1. Process for co-producing methanol, ammonia and urea from a hydrocarbon feedstock, said process comprising the steps of a) from a first methanol process, comprising a first reforming step and first methanol conversion step obtaining a first effluent comprising methanol and a first gas effluent comprising hydrogen, nitrogen and unconverted carbon oxides, and from a second methanol processes, comprising a second reforming step and a second methanol conversion step obtaining a second effluent comprising methanol and a second gas effluent comprising hydrogen, nitrogen and unconverted carbon oxides; b) producing an ammonia synthesis gas from the first and/or second gas effluent in a common catalytic methanation stage and withdrawing said ammonia synthesis gas preferably having a H.sub.2:N.sub.2 molar ratio of approximately 3:1; c) catalytically converting the nitrogen and hydrogen of the ammonia synthesis gas in a common ammonia synthesis stage and withdrawing an effluent comprising ammonia and a purge-gas stream comprising hydrogen, nitrogen and/or methane; and d) reacting at least part of the effluent comprising ammonia with at least part of a flue gas comprising CO2 from at least one of the first and second reforming steps to produce urea.

2. Process according to claim 1, wherein in each of the first and second methanol processes, the following steps are carried out: 1) producing a methanol synthesis gas containing hydrogen, carbon oxides and nitrogen by steam reforming the hydrocarbon feedstock in a reforming section comprising a primary and a secondary reforming stage; 2) catalytically converting the carbon oxides and hydrogen of the methanol synthesis gas in a once-through methanol synthesis stage and withdrawing an effluent comprising methanol and a gas effluent comprising nitrogen, hydrogen and unconverted carbon oxides;

3. Process according to claim 2 wherein the secondary reforming stage is an air-blown secondary reforming stage.

4. Process according to claim 1, wherein the hydrocarbon feedstock is natural gas or substitute natural gas (SNG) or a gas comprising >80% methane.

5. Process according to claim 1, wherein the methanol conversion of the first and second once-through methanol synthesis stage of the first and the second methanol processes are controlled at least by controlling the amount of syngas from the first and/or second reforming step fed to the first and/or second methanol production stage.

6. Process according to claim 1, wherein the methanol synthesis is conducted by passing the synthesis gas through one or more boiling water reactor and subsequently through one or more adiabatic fixed bed reactors.

7. Process according to claim 1, wherein the methanol synthesis is conducted by passing the synthesis gas through one or more boiling water reactor and subsequently through one or more gas cooled reactors.

8. Process according to claim 7 wherein the boiling water reactor is in the form of a single reactor of the condensing-methanol type which comprises within a common shell a fixed bed of methanol catalyst particles and cooling means adapted to indirectly cooling the methanol synthesis gas with a cooling agent.

9. Process according to claim 7, further comprising cooling the synthesis gas withdrawn from each methanol reactor to condense methanol and passing the gas through a separator, withdrawing a bottom fraction from the separator containing the raw methanol, withdrawing an overhead fraction containing synthesis gas which is passed to the subsequent methanol reactor, and forming a single liquid effluent containing methanol by combining the bottom fractions of the separators of each reactor containing the raw methanol.

10. Process according to claim 1, further comprising withdrawing a hydrogen-rich stream from the purge-gas stream comprising hydrogen, nitrogen and methane and adding this stream to step (a).

11. Process according to claim 1, further comprising withdrawing an off gas from the purge-gas stream comprising hydrogen, nitrogen and methane and adding this stream to step (a) as fuel.

12. Process according to claim 1, comprising further parallel methanol processes.

13. Process according to claim 1, wherein at least a part of the methanol from the first and/or second methanol process is converted into formaldehyde.

14. Process according to claim 13 wherein the formaldehyde is absorbed into aqueous urea solution based on at least part of the urea to produce UFC85.

15. Process according to claim 13, wherein the UFC85 is added to the urea as a coating.

16. Plant comprising a first and a second parallel methanol process lines, at least one common methanation reactor and at least one common ammonia synthesis step.

17. Plant according to claim 16, further comprising an interconnecting synthesis line allowing fluid communication between the first and second methanol process line.

18. Plant according to claim 16, further comprising a urea production section.

19. Plant according to claim 16, further comprising a formaldehyde production section.

20. Plant according to claim 16, further comprising a UFC85 production section.

21. Plant comprising a first and a second parallel methanol process lines, at least one common methanation reactor and at least one common ammonia synthesis step arranged to carry out the process according to claim 1.

Description

[0052] The accompanying figure shows a simplified block diagram of the process according to a specific embodiment of the invention including reforming, methanol synthesis stage, methanation stage and ammonia synthesis stage.

[0053] In first reforming section, natural gas 1 is added to primary reforming stage 20 (steam methane reformer) under addition of steam 2. The partly reformed gas is then further reformed in air-blown secondary reforming stage 21 (auto-thermal reformer) under addition of air 3. The methanol synthesis gas 4 containing hydrogen, carbon oxides and nitrogen is cooled in waste heat boiler(s) under the production of steam and then compressed to methanol synthesis pressure (not shown). In first methanol synthesis stage 22 the methanol synthesis gas 4 is converted in once-through operation (single-pass operation, no recirculation) under the production of a liquid effluent 5 containing methanol and a gas effluent 6 containing nitrogen, hydrogen and unconverted carbon oxides. Approximately 80 wt % of the total plant capacity goes to the production of methanol of effluent 5.

[0054] In second reforming section, natural gas 1B is added to primary reforming stage 20B (steam methane reformer) under addition of steam 2B. The partly reformed gas is then further reformed in air-blown secondary reforming stage 21B (autothermal reformer) under addition of air 3B. The methanol synthesis gas 4B containing hydrogen, carbon oxides and nitrogen is cooled in waste heat boiler(s) under the production of steam and then compressed to methanol synthesis pressure (not shown). In second methanol synthesis stage 22B the methanol synthesis gas 4B is converted in once-through operation (single-pass operation, no recirculation) under the production of a liquid effluent 5B containing methanol and a gas effluent 6B containing nitrogen, hydrogen and unconverted carbon oxides. Approximately 80 wt % of the total plant capacity goes to the production of methanol of effluent 5B.

[0055] The carbon oxides in gas effluents 6 and 6B are hydrogenated to methane in the common methanation stage 23 thereby generating an ammonia synthesis gas 7 having a H.sub.2:N.sub.2 molar ratio of 3:1. The ammonia synthesis gas 7 is then passed through ammonia synthesis stage 24 under the production of an effluent 8 containing ammonia and an effluent stream 9 containing hydrogen, methane and nitrogen which is treated to give two effluent streams. First effluent stream 11 is returned as off-gas fuel to the primary reforming stage 20. Second effluent stream 10, a hydrogen-rich stream (>90 vol % H.sub.2) being returned to the methanol synthesis stage 22 by combining with the methanol synthesis stream 4. Approximately 20 wt % of the total plant capacity goes to the production of ammonia in effluent 8. The plant obviates the use of Air Separation Units (ASU) as well as water gas shift and CO.sub.2-removal stages.

[0056] The following table shows the temperatures, pressures and flow rates of the different streams for a process according to FIG. 1 where we are able to produce approximately 3000 MTPD methanol and 750 MTPD ammonia despite the use of a difficult feedstock. The feedstock used is heavy natural gas (85 vol % methane):

TABLE-US-00001 TABLE Temp. Flow rate/kmol/h Position C. Pressure Bar g H.sub.2O H.sub.2 N.sub.2 CH.sub.4 CO CO.sub.2 Ar 4, 4B 947 30.1 5890 12023 1414 419 3147 1043 16 6, 6B 35 120.3 2.7 4574 1457 463 17 38 20 7 35 119.3 8742 2914 1036 40 10, 10B 35 32 1463 66 61 4 11, 11B 35 12 167 477 450 16

[0057] The process air compressor 25 can be one common or one for each reforming section.

[0058] Stream 4/4B can be distributed to the methanol processes 22/22B depending on individual catalyst activity in order to optimize OPEX via the line 12.

[0059] Hydrogen rich stream 10/10B and off-gas 11/11B can be distributed to optimize the process requirements in reforming sections and methanol synthesis sections.

[0060] By the nature of the co-production of methanol and ammonia from natural gas, there will not be significant amount of CO.sub.2 available in the process gas to be recovered for urea production. If it is desired to use part or all the ammonia production in the presented process, then CO.sub.2 from the flue gas from one or more reforming sections can be recovered in a CO2 removal section 27.

[0061] There would typically be sufficient of CO2 in the flue gas from one reforming section to convert all the ammonia from the combined methanol section effluent gas into urea. Thereby an economy of scale can be achieved for the urea plant, section 29.

[0062] A widely used coating material in urea production is urea-formaldehyde-concentrate (UFC85) containing up to 85% urea+formaldehyde and balance is water, in order to avoid caking of urea product. The synergy for production of the coating material in this invention is clear since a small stream of methanol 16 is used to produce formaldehyde and urea solution is required for the absorption of formaldehyde to produce UFC85 or more diluted UFC products in section 28.