Catalytic gasification to produce ammonia and urea

• US 10,618,818 B1
• Filed: 03/22/2019
• Issued: 04/14/2020
• Est. Priority Date: 03/22/2019
• Status: Active Grant

• Current Assignee: Sure Champion Investments Limited
• Original Assignee: Sure Champion Investments Limited
• Inventors: Sirdeshpande, Avinash
• Primary Examiner(s): Bonaparte, Amy C
• Application Number:
  US16/361,448
• Time in Patent Office: 389 Days
• Field of Search: None
• CPC Class Codes: B01J 21/04 Alumina
• CPC Class Codes: B01J 23/04 Alkali metals
• CPC Class Codes: B01J 23/92 of catalysts comprising metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
• CPC Class Codes: B01J 38/68 including substantial dissolution or chemical precipitation of a catalyst component in the ultimate reconstitution of the catalyst
• CPC Class Codes: C01B 2203/0255 containing a non-catalytic partial oxidation step
• CPC Class Codes: C01B 2203/0261 containing a catalytic partial oxidation step [CPO]
• CPC Class Codes: C01B 2203/0288 containing two CO-shift steps
• CPC Class Codes: C01B 2203/0415 Purification by absorption in liquids
• CPC Class Codes: C01B 2203/0475 the impurity being carbon dioxide
• CPC Class Codes: C01B 2203/0495 the impurity being water
• CPC Class Codes: C01B 2203/068 Ammonia synthesis
• CPC Class Codes: C01B 2203/0894 Generation of steam
• CPC Class Codes: C01B 3/025 Preparation or purification of gas mixtures for ammonia synthesis
• CPC Class Codes: C01B 3/36 using oxygen or mixtures containing oxygen as gasifying agents
• CPC Class Codes: C01B 3/386 Catalytic partial combustion
• CPC Class Codes: C01B 3/48 followed by reaction of water vapour with carbon monoxide
• CPC Class Codes: C01C 1/0405 from N2 and H2 in presence of a catalyst
• CPC Class Codes: C01C 1/047 by condensation
• CPC Class Codes: C01C 1/0488 Processes integrated with preparations of other compounds, e.g. methanol, urea or with processes for power generation
• CPC Class Codes: C07C 273/04 from carbon dioxide and ammonia
• CPC Class Codes: C07C 273/10 : combined with the synthesis of ammonia
• CPC Class Codes: C10J 2200/06 : Catalysts as integral part of gasifiers catalysts added to the feed C10J2300/0986
• CPC Class Codes: C10J 2300/0986 : Catalysts
• CPC Class Codes: C10J 2300/1668 : to urea preparation of urea C07C273/00; to ammonia preparation of ammonia C01C1/0405
• CPC Class Codes: C10J 2300/1807 : Recycle loops, e.g. gas, solids, heating medium, water
• CPC Class Codes: C10J 3/34 : Grates; Mechanical ash-removing devices
• CPC Class Codes: C10J 3/482 : Gasifiers with stationary fluidised bed
• CPC Class Codes: C10J 3/72 : Other features
• CPC Class Codes: C10K 3/005 : by partial oxidation
• CPC Class Codes: Y02P 20/52 : using catalysts, e.g. selective catalysts
• CPC Class Codes: Y02P 20/584 : Recycling of catalysts

Abstract

The present invention provides a process for preparing higher-value products from carbonaceous feedstocks. The process includes converting carbonaceous feedstock in a hydromethanation reactor to a methane-enriched raw product stream, converting the methane-enriched raw product stream to an ammonia synthesis feed gas, then converting the ammonia synthesis feed gas to higher-value products such as ammonia and urea.

Claims

1. A process for generating an ammonia synthesis gas from a non-gaseous carbonaceous material and a hydromethanation catalyst, the process comprising the steps of:

a) preparing a carbonaceous feedstock from the non-gaseous carbonaceous material;

b) introducing the carbonaceous feedstock, the hydromethanation catalyst, high-pressure, superheated steam, and oxygen into a hydromethanation reactor;

c) reacting the carbonaceous feedstock in the hydromethanation reactor at an operating temperature from about 800°

F. (about 427°

C.) up to about 1500°

F. (about 816°

C.), and an operating pressure of at least about 250 prig (about 1825 kPa), to produce a by-product char, and a methane-enriched raw product gas comprised of methane, carbon monoxide, hydrogen, carbon dioxide, hydrogen sulfide, ammonia, steam, heat energy and entrained solids;

d) removing a substantial portion of the entrained solids from the methane-enriched raw product gas stream to generate a solids-depleted, methane-enriched raw product gas stream and a recovered primary solids stream;

e) removing any fine particulate matter remaining in the solids-depleted, methane-enriched raw product gas stream to generate a fines-cleaned, methane-enriched raw product gas stream and a recovered secondary fines stream;

f) withdrawing a stream of the by-product char from the hydromethanation reactor as the by-product char stream, wherein the by-product char stream comprises a carbon content and entrained hydromethanation catalyst; and

g) generating the ammonia synthesis gas by;

i) reacting the fines-cleaned, methane-enriched raw product gas stream with an oxidant comprised of air, secondary oxygen and optionally secondary high-pressure steam to convert a substantial portion of the methane to a raw ammonia synthesis gas comprised of nitrogen, hydrogen, carbon monoxide, carbon dioxide and methane;

ii) cooling the raw ammonia synthesis gas to generate steam and a cooled gas comprising fine particulate matter;

iii) removing the fine particulate matter from the cooled gas to generate a particle-depleted cooled gas;

iv) shifting the particle-depleted cooled gas with steam to convert a substantial portion of the carbon monoxide to form a hydrogen-enriched raw product gas;

v) recovering the ammonia present in the hydrogen-enriched raw product gas to generate an ammonia-depleted effluent;

vi) removing a substantial portion of the carbon dioxide and a substantial portion of the hydrogen sulfide from the ammonia-depleted effluent to produce a sweetened gas stream and a carbon dioxide-enriched product; and

vii) converting the carbon monoxide and carbon dioxide in the sweetened gas to methane by reaction with hydrogen to produce the ammonia synthesis gas wherein the ammonia synthesis gas is comprised of hydrogen and nitrogen and is substantially free of carbon oxides.

2. The process of claim 1, further comprising the step of generating an ammonia product stream from the ammonia synthesis gas.

3. The process of claim 2, further comprising the step of converting a portion of the ammonia product stream to urea using the carbon dioxide-enriched product.

4. The process of claim 2, wherein the process has a steam demand and a power demand that are met by internal energy integration such that the process requires no net import of steam or power.

5. The process of claim 3, wherein the process has a steam demand and a power demand that are met by internal energy integration such that the process requires no net import of steam or power.

6. The process of claim 3, wherein the carbon dioxide-enriched product is sufficient to satisfy the requirements for urea synthesis.

7. The process of claim 1, wherein the hydromethanation catalyst comprises an alkali metal.

8. The process of claim 7, wherein the alkali metal is potassium.

9. The process of claim 1, further comprising treating all or a portion of the by-product char stream in a catalyst recovery unit comprising a quench tank and a quench medium, the treatment comprising the steps of:

a) quenching the by-product char stream with the quench medium to extract a portion of the entrained catalyst to generate a catalyst-depleted char and a liberated hydromethanation catalyst;

b) withdrawing a stream of catalyst-depleted char from the catalyst recovery unit as the catalyst-depleted char stream; and

c) withdrawing a stream of the liberated hydromethanation catalyst from the catalyst recovery unit as a recovered hydromethanation catalyst stream.

10. The process of claim 9, further comprising the step of feeding at least a portion of the recovered secondary fines stream removed from the solids-depleted, methane-enriched raw product gas stream to the catalyst recovery unit.

11. The process of claim 9, wherein the hydromethanation catalyst comprises at least a portion of the recovered hydromethanation catalyst stream.

12. The process of claim 1, wherein the ammonia synthesis gas is generated in step g) step i) by a partial oxidation process using a combination of air and oxygen as an oxidant.

13. The process of claim 12, wherein the ammonia synthesis gas has a hydrogen to nitrogen molar ratio in the range of 3 to 3.5.